Additive comprising low surface energy group and hydroxyl groups and coating compositions

ABSTRACT

Additives comprising a low surface energy group and one or more hydroxyl groups are described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/381,382, filed Aug. 27, 2014, now U.S. Pat. No. 9,441,135, which is anational stage filing under 35 U.S.C. 371 of International ApplicationNo. PCT/US2013/043306, filed May 30, 2013, which claims benefit of U.S.Provisional Application No. 61/661,541 filed Jun. 19, 2012.

BACKGROUND OF THE INVENTION

WO2008/067262 describes optical substrates having a surface layer thatcomprises the reaction product of a polymerizable mixture comprising atleast one perfluoropolyether material comprising at least twofree-radically polymerizable groups and at least one segment withgreater than 6 ethylene oxide repeat units; and at least onenon-fluorinated binder precursor comprising at least two free-radicallypolymerizable groups.

U.S. Pat. No. 7,153,563 describes a hard coat film comprising asubstrate film and a hard coat layer disposed at least on one face ofthe substrate film, wherein the hard coat layer comprises 100 parts byweight of (A) a resin of an ionizing radiation curing type and 0.1 to 10parts by weight of (B) a non-ionic surfactant. The hard coat film isused for protection of surfaces such as the surface of touch panels anddisplays. Attachment of fingerprints during input operations by fingerson the surfaces is suppressed and the attached fingerprints can beeasily wiped out. Scratch resistance and wear resistance of conventionalhard coat films are retained.

As described in the “Description of Related Art” in U.S. Pat. No.7,153,563, to provide the property of preventing attachment of dirt andremoving the attached dirt, it is frequently conducted that asilicone-based compound or a fluorine-based compound is added toconventional hard coat films having a hard coat layer which is formedand supported on a substrate film by curing by heating or with anionizing radiation. However, the highly water-repellent surface obtainedabove does not always suppress the attachment of fingerprints and theattached fingerprints are more clearly visible. Conventional hard coatfilms have a drawback in that fingerprints are attached on the filmsafter input operations with fingers and the attached fingerprints arenot easily wiped out.

Certain fluorinated additives have been found to provide low lintattraction, as determined by use of a Cellulose Surface Attraction Test,as described in WO2008/067262 and WO2009/076389.

Certain silicone additives have also been found to provide low lintattraction as described in WO 2009/029438. Such silicone (meth)acrylateadditives generally comprise a polydimethylsiloxane (PDMS) backbone andat least one alkoxy side chain terminating with a (meth)acrylate group.The alkoxy side chain may optionally comprise at least one hydroxylsubstituent. Such silicone (meth)acrylate additives are commerciallyavailable from various suppliers such as Evonik under the tradedesignations “TEGO Rad”.

US Patent Application Publication No. US2012/0154811 describes coatingcompositions comprising non-ionic surfactant and “TEGO Rad 2100”. Inaddition to low lint attraction, such cured coatings also exhibit aproperty of an initially visible simulated fingerprint reducing invisibility after a duration of time. However, as evident by Examples34-45 of US Patent Application Publication No. US2012/0154811, as thelint attraction decreases (low cellulose surface attraction), thefingerprint visibility ratio increases. Thus, industry would findadvantage in coating combinations that can provide a combination of lowlint attraction and low fingerprint visibility.

SUMMARY OF THE INVENTION

Presently are described coating compositions comprising a non-ionicsurfactant and an additive wherein the additive comprises a low surfaceenergy group and one or more hydroxyl groups. The cured coating canexhibit reduced fingerprint visibility and low cellulose surfaceattraction. Also described are copolymer compositions useful asadditives.

In some embodiments, a coating composition is described comprising apolymerizable resin composition; a non-ionic unpolymerizable surfactanthaving an hydrophilic lipophilic balance ranging from 2 to 6 andoptionally a polymerizable surfactant wherein the surfactants arepresent at a concentration of greater than 10 wt-% to 25 wt-% solids;and an additive. In one embodiment, the additive comprises a low surfaceenergy group and one or more hydroxyl groups with the proviso that theadditive does not consist of an additive having a polydimethylsiloxanebackbone and a hydroxyl substituted side chain terminating with anacrylate group. In another embodiment, the additive comprises a lowsurface energy group and hydroxyl groups wherein at least a portion ofthe hydroxyl groups are primary hydroxyl groups. The low surface energygroup generally comprises a fluorinated or silicone moiety.

In other embodiments, copolymer compositions that are useful asadditives are described. In one embodiment, the additive has the generalformula:-[M^(L)]_(l)-[M^(OH)]_(q)-[M^(A)]_(p)-[M^(R4)]_(o)— wherein l, q, p, ando are at least 1;or-[M^(L)]_(l)-[M^(OH)]_(q)-[M^(A)]_(p)-[M^(R4)]_(o)-[M^(AO)]_(n)— whereinl, q, p, o and n are at least 1;wherein[M^(L)] represent units derived from one or more ethylenicallyunsaturated monomers comprising a low surface energy silicone orfluorinated group;[M^(OH)] represent units derived from one or more ethylenicallyunsaturated monomers and at least one hydroxyl group;[M^(A)] represent units comprising a residue of [M^(OH)] and afree-radically polymerizable group;[M^(R4)] represent units derived from one or more ethylenicallyunsaturated monomers comprising an alkyl group; and

[M^(AO)] represents units derived from one or more ethylenicallyunsaturated monomers having the group R—(O—R_(a))_(j) wherein R is analkyl group having greater than 6, 7, or 8 carbon atoms, Ra isindependently an alkylene group C_(x)H_(2x) where x=2 to 4, and j rangesfrom 1 to 50.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a digital photograph of a human fingerprint applied to acured coating at a microscope setting of 12× (1.2× objective and a 10×multiplier).

FIG. 1B is a digital photograph of the human fingerprint applied to thecured coating of FIG. 1A five minutes later.

FIG. 2A is a digital photograph of a human fingerprint applied to acured coating at a microscope setting of 500×.

FIG. 2B is a digital photograph of the human fingerprint applied to thecured coating of FIG. 2A four minutes later.

FIGS. 3A and 3B are illustrations of the photographs of FIGS. 2A and 2Brespectively.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS

The coating compositions described herein comprise a lipophilic liquid,such as a (e.g. non-ionic) surfactant. Such (e.g. non-ionic) surfactantis typically an unpolymerizable surfactant, meaning that the surfactantis not reacted or copolymerized with the other components of the coatingcomposition. Hence, the (e.g. non-ionic) surfactant is unpolymerized inthe cured coating composition. The (e.g. non-ionic) surfactant can alsobe characterized as “free” surfactant. In some embodiments, the coatingcompositions further comprise an unpolymerizable surfactant incombination with a polymerizable surfactant.

The coating composition further comprises an additive comprising a lowsurface energy group, such as a silicone group or a fluorinated groupand a hydroxyl group. The inclusion of the (e.g. primary) hydroxylgroups are surmised to provide the low lint attraction, as measured bythe Cellulose Surface Attraction Test, described in the forthcomingexamples. The cured surface layers preferably have a haze of less than20%, more preferably less than 10% and even more preferably less than5%, 4%, 3%, 2%, or 1% according to the Cellulose Surface AttractionTest.

In favored embodiments, the additive further comprises a free-radicallypolymerizable group (derived from the hydroxyl group) and an alkylgroup. In some embodiments, the alkyl group of the additive is ahydrophobic group. In some embodiments, the hydrophobic group of theadditive can be derived from a non-ionic surfactant. Unless specifiedotherwise, the following description pertaining to non-ionic surfactantsis applicable to both the unpolymerizable surfactant of the coatingcomposition as well as the surfactant from which the hydrophobic groupof the additive can be derived.

Non-ionic surfactants are organic compounds that are amphiphilic,comprising a hydrophobic group (or “tail”) and a hydrophilic group (or“head”). Typically surfactant molecules migrate to the surface, wherethe hydrophobic group may extend out of the bulk coating phase, whilethe water soluble head group remains in the bulk coating phase. Thisalignment and aggregation of surfactant molecules at the surface acts toalter the surface properties of the coating.

A surfactant can be classified by the presence of formally chargedgroups in its head. The head of an ionic surfactant carries a netcharge. A non-ionic surfactant has no charged groups in its head.

Surfactants can be characterized by various methodologies. One commoncharacterization method, as known in the art, is thehydrophilic-lipophilic balance (“HLB”). Although various method havebeen described for determining the HLB of a compound, unless specifiedotherwise, as used herein HLB refers to the value obtained by theGriffin's method (See Griffin WC: “Calculation of HLB Values ofNon-Ionic Surfactants,” Journal of the Society of Cosmetic Chemists 5(1954): 259). The computations were conducted utilizing the softwareprogram Molecular Modeling Pro Plus from Norgwyn Montgomery Software,Inc. (North Wales, Pa.).

According to Griffin's method:HLB=20*Mh/Mwhere Mh is the molecular mass of the hydrophilic portion of themolecule, and M is the molecular mass of the whole molecule. Thiscomputation provides a numerical result on a scale of 0 to 20, wherein“0” is highly lipophilic.

Griffin's method is typically used to calculate the HLB of a singlemolecule. However, various (e.g. commercially available) non-ionicsurfactants comprise a mixture of molecules. When the surfactantcomprises a mixture of molecules, the HLB can be calculated by thesummation of the HLBs of the individual molecules multiplied by theweight fraction of each molecule.

A broad range of non-ionic surfactants may be utilized as the startingcomponent in the synthesis of the additive. Without intending to bebound by theory, the additive is believed to act a compatibilizer forthe “free” surfactant that is unpolymerized in the cured coatingcomposition. The HLB of surfactants for use as a starting component inthe synthesis of the additive may range from 1 to 19. The non-ionicsurfactant utilized as the starting component in the synthesis of theadditive is typically free of fluorine and silicone atoms.

The unpolymerizable (e.g. non-ionic) surfactant of the coatingcomposition is more lipophilic then hydrophilic, i.e., an HLB less than10. In favored embodiments, the HLB is at least 2 or 2.5 and no greaterthan about 6 or 5.5. In some favored embodiments, the coatingcomposition comprises a (e.g. non-ionic) surfactant having an HLB of atleast 3, or 3.5, or 4.0. The unpolymerizable (e.g. non-ionic) surfactantof the coating composition is typically not a lipolytic enzyme, such aslipase. Lipolytic enzymes are generally more hydrophilic than lipophilichaving an HLB greater than 6. Without intending to be bound by theory itis surmised that the lipophilic group of the surfactant may physicallyabsorb the body oil of a fingerprint.

Such (e.g. non-ionic) surfactants generally comprise an alkyl or alkenylgroup having at least 12, or 14, or 16, or 18 carbon atoms. Suchrelatively long chain alkyl or alkylene group is commonly referred to asa “fatty” group. The number of carbon atoms can be greater than 18carbon atoms provided the (e.g. non-ionic) surfactant is a liquid atambient temperature (e.g. 25° C.). The liquid (e.g. non-ionic)surfactant may further comprise up to 20 wt-% of a solid fraction. Insome embodiments, the alkyl or alkenyl group has no greater than 24carbon atoms. In some favored embodiments, such alkyl group isunbranched. The alkyl or alkenyl group may optionally comprisesubstituents, provided that the (e.g. non-ionic) surfactant issufficiently lipophilic, e.g. having an HLB as previously described. Theunpolymerizable non-ionic surfactant is also typically free of fluorineand silicone atoms.

Surfactants having the preferred HLB range (e.g. by inclusion of a fattygroup) are generally non-ionic surfactants. However, other classes ofsurfactants may also be suitable provided such surfactant issufficiently lipophilic as described herein.

Various classes of non-ionic surfactants are known including for examplefatty alcohols, fatty acids, fatty amines, fatty amides, and derivativesthereof.

In some embodiments, such as for use as a starting compound in thesynthesis of the additive, the non-ionic surfactant is a fatty alcohol.Fatty alcohols typically have the general formulaR—OHwherein R is a (e.g. straight or branched chain) alkyl or alkenyl group,as previously described, optionally substituted in available positionsby N, O, or S atoms. Various fatty alcohols are known including dodecylalcohol, cetyl alcohol CH₃(CH₂)₁₅OH, stearyl alcohol (also known asoctadecyl alcohol or 1-octadecanol), and oleyl alcohol.

In some embodiments, the non-ionic surfactant is a derivative of a fattyalcohol. One favored derivative is a fatty alcohol, ester or derivativethereof comprising repeat units of ethylene oxide and/or repeat units ofpropylene oxide. Such derivatives may also be referred to as apolyethoxylated and/or polypropoxylated fatty alcohols, esters, orderivatives thereof. Such derivatives are a favored unpolymerizablenon-ionic surfactant of the coating composition and can also be utilizedas a starting compound in the synthesis of the additive. Oneillustrative commercially available surfactant of this type is availablefrom Croda as “Brij O2”, reported to have an HLB of 4.9. Suchpolyethoxylated alcohol comprises a mixture of molecules having thegeneral formulaC₁₈H₃₅(OCH₂CH₂)_(n)OHIf “n” were 1, such structure has a calculated HLB of 3.6. Further, if“n” were 2, such structure has a calculated HLB of 5.4. If “n” were 0,such structure (i.e. oleyl alcohol) has a calculated HLB of 1.1.

In other embodiments, the non-ionic surfactant is a derivative of afatty acid. Fatty acids typically have the formulaRC(O)OHwhere R is a (e.g. straight chain) alkyl or alkenyl group, as previouslydescribed

One class of fatty acid derivative can be prepared by reacting a fattyacid with a short chain alkyl glycol mono alkyl ether. Illustrativenon-ionic surfactants of this type are described in the following table.

Surfactant HLB Reaction product of oleic acid and diethylene glycol 4.7mono-ethyl ether Reaction product of oleic acid and dipropylene glycol2.8 mono-methyl ether Reaction product of oleic acid and triethyleneglycol 6.2 mono-ethyl ether Reaction product of oleic acid andtriethylene glycol 5.1 mono-n-butyl ether Reaction product of oleic acidand 1-methoxy-2-propanol 2.0 Reaction product of oleic acid and ethyleneglycol mono- 3.1 methyl ether

Such derivatives having a HLB no greater than 6, as previouslydescribed, are also favored unpolymerizable non-ionic surfactants of thecoating composition and can also be utilized as a starting compound inthe synthesis of the additive. Derivatives having HLB values of 6 orgreater can be utilized in the synthesis of the additive.

The molecular weight of the (e.g. free) surfactant is typically at least150 g/mole and generally no greater than 600 g/mole. In someembodiments, the molecular weight of the surfactant is at least 200g/mole, 250 g/mole, or 300 g/mole.

The non-ionic surfactant is preferably present in an amount greater than10 wt-% solids of the coating composition. The term “wt-% solids” refersto the total non-volatile components of the coating composition. In someembodiments, the concentration of non-ionic surfactant is at least 11wt-% or 12 wt-%. or 13 wt-% or 14 wt-%. In yet other embodiments, theconcentration of non-ionic surfactant is 15 wt-%, 16 wt-%, or 17 wt-%.The concentration of the non-ionic surfactant is typically no greaterthan 25 wt-% and in favored embodiments no greater than 20 wt-%.

In some embodiments, the coating composition further comprises a (e.g.free-radically) polymerizable non-ionic surfactant in combination withthe unpolymerized surfactant. In this embodiment, the concentration ofpolymerizable and unpolymerizable non-ionic surfactant is greater than10 wt-% solids of the coating composition and typically no greater than30 wt-%, or 25 wt-%, 20 wt-%. The inclusion of a (e.g. free-radically)polymerizable non-ionic surfactant is amenable to compatibilizing thefree surfactant. The inclusion of such can provide higher concentrationsof free surfactant in combination with lower haze (as compared to thesame concentration of free surfactant without a polymerizablesurfactant). The (e.g. free-radically) polymerizable non-ionicsurfactant may be present in the coating composition at a concentrationof at least 1, or 2, or 3 wt-%. In some embodiments, the concentrationof (e.g. free-radically) polymerizable non-ionic surfactant is nogreater than the concentration of free surfactant. In some embodiments,the weight ratio of free surfactant to polymerizable surfactant is atleast 1.5:1 or 2:1.

Polymerizable surfactants have been described in the art. A non-ionicsurfactant comprising a (meth)acrylate group can be formed by reactingthe hydroxyl group of the previously described fatty alcohol derivativeswith a (meth)acrylic acid or a (meth)acryloyl halide, or functional(meth)acrylate compound such as an isocyanato-functional (meth)acrylatecompound. Replacing a single hydroxyl group with a (meth)acrylate grouptypically does not significantly change the HLB. Thus, the HLB of thepolymerizable surfactant is about the same as the HLB of theunpolymerizable surfactant from which the polymerizable surfactant wasderived. In some embodiments, the polymerizable surfactant has an HLBranging from 2 to 13.

A polymerizable surfactant generally comprises a hydrophobic group, ahydrophilic group and a (free-radically) polymerizable group. In someembodiments, the polymerizable surfactant has the general formula:R(OCH₂CH₂)_(n)OC(O)—C(R⁶)H═CH₂wherein R is a fatty group, as previously described, and n is the numberof ethylene oxide repeat units, and R⁶ is hydrogen or alkyl having from1 to 4 carbon atoms. In some embodiments, n is at least 1, 2, or 3 andon average is no greater than 20, 19, 18, 17, 16, 15, 14, 13, 12, or 10.In some embodiments, the polymerizable surfactant comprises a mixture ofmolecules wherein n is 1 and n is 2. In some embodiments R is an alkylgroup having at least 12, or 14, or 16, or 18 carbon atoms.

Polymerizable surfactants of this type may be obtained by reaction of apolyethoxylated alcohol, R(OCH₂CH₂)_(n)OH, with an (meth)acryloyl acidchloride, methacrylic or acrylic acid, or a (meth)acrylic anhydride.

In some embodiments, the polymerizable surfactant has the generalformula:R(OCH₂CH₂)_(n)OC(O)N(H)—CH₂-Q-[O—C(O)C(R⁶)H═CH₂]_(z)wherein R is a fatty group, as previously described, Q is a connectinggroup having a valency of at least 2, R⁶ is hydrogen or alkyl havingfrom 1 to 4 carbon atoms, and z is 1 or 2.

Polymerizable surfactants of this type may be obtained by reaction of anisocyantoalkyl (meth)acrylates, such as isocyanatoethyl acrylate,isocyanatoethyl methacrylate, or 1,1-bis(acryloyloxymethyl) ethylisocyanate, with the polyethoxylated alcohol, R(OCH₂CH₂)_(n)OH.

The coating composition described herein comprises an additivecomprising a low surface energy group, such as a silicone or fluorinatedgroup and hydroxyl groups. The additive may be present in an amount ofat least 0.01, or 0.05, or 0.10, or 0.20, or 0.30, or 0.5 wt-% solidsranging up to about 10 wt-% solids of the coating composition. In someembodiments, the concentration of additive is no greater than about 5wt-%, 4 wt-% or 3 wt-% or 2 wt-% or 1 wt-% solids of the coatingcomposition.

In some embodiments, the inclusion of the additive provides lowerfingerprint visibility as a function of time at the same surfactantconcentration. In this embodiment, the coating composition furthercomprising the additive may have the same non-ionic surfactantconcentration as previously described. The additive may also allow forhigher concentrations of the non-ionic surfactant with lower haze.

In other embodiments, lower fingerprint visibility as a function of timemay be achieved with lower concentrations of surfactant by inclusion ofthe additive. In this embodiment, the concentration of surfactant may belower than 10 wt-%. For example, the minimum concentration of non-ionicsurfactant may be 5 wt-%, or 6 wt-%, or 7 wt-%, or 8 wt-%, or 9 wt-%.However in favored embodiments, the coating composition comprisesgreater than 10 wt-% of non-ionic surfactant in combination with anadditive having a hydroxyl group and a low surface energy group, such asa silicone group or fluorinated group.

The visibility of a fingerprint initially or as a function of time canbe determined by various methods. Preferably, however, such assessmentis made using a reproducible standardized method. One method ofdetermining the fingerprint visibility of a coating compositioncomprises providing a coating composition on a substrate, applying asimulated fingerprint composition onto the coated substrate, and

measuring an optical property of the simulated fingerprint compositionon the coated substrate. If the measured optical property is for exampletransmission or haze, the substrate to which the coating composition isapplied is a light-transmissible (e.g. transparent) substrate. However,if the optical property is for example gloss, the substrate mayalternatively be an opaque substrate.

The simulated fingerprint composition is generally a highly lipophilicsubstance. The simulated fingerprint composition is typically a mixtureof a fatty substance that is predominantly a solid at ambienttemperature (25° C.) and an oily substance that is predominantly aliquid at ambient temperature (25° C.). Vegetable shortening is asuitable solid; whereas a fatty alkyl oxide wherein the alkyl group hasat least 24 carbon atoms, such as available from Sigma under the tradedesignation “Triolein”, is a suitable liquid. The simulated fingerprintmay be applied to the (i.e. cured) coating using a variety oftechniques. The oily substance may be diluted with for example a (e.g.alcohol) solvent in order to reduce the viscosity and evenly apply athin coating (e.g. a thickness of 1.2 microns). A rubber stopper canconveniently be used to provide a continuous coating. However, otherrubber stamp designs, or a sandpaper roughened rubber stopper or surfacecould be utilized to provide a discontinuous coating.

For embodiments wherein the coating composition is a polymerizablecomposition, the coating composition is cured prior to applying thesimulated fingerprint. For embodiments wherein the coating compositioncomprises a solvent, the coating composition is dried prior to applyingthe simulated fingerprint.

The optical property, such as haze may be measured initially and after aduration of time. The duration of time may be 1, 2, 3, 4, or 5 minutesor longer durations of times, such as 20 minutes. One suitable methodfor determining fingerprint visibility is described in greater detail inthe forthcoming examples.

By comparing the initial (e.g. simulated) fingerprint visibility to thevisibility after a duration of time (e.g. 20 minutes), one can calculatea ratio by dividing the visibility after a duration of time by theinitial visibility. When the ratio is 1, there is no change in thevisibility of a (e.g. simulated) fingerprint as a function of time. Asthe ratio, becomes smaller, the change is visibility (i.e. fading of thefingerprint) become greater. In some embodiments, the cured coatingdescribed herein exhibits a ratio of simulated fingerprint visibilityafter a duration of time (e.g. at 20 minutes) to initial simulatedfingerprint visibility of less than 0.80, or 0.70, or 0.60, or 0.50.

The visibility of an actual or simulated fingerprint initially or as afunction of time can also be determined by use of visible inspection.For example, with reference to FIG. 1A and FIG. 1B, the visibility of afingerprint can be captured by use of a microscope equipped with adigital camera, using various magnifications. With reference to FIG. 1A,a fingerprint is initially highly visible at a magnification of forexample 12×. However, with reference to FIG. 1B, this same fingerprintis substantially less visible after a duration of time (e.g. 5 minutes).With reference to FIG. 2A, at an even high magnification of for example500×, oil droplets of the fingerprint are initially evident on the curedcoating surface. However, with reference to FIG. 2B, these oil dropletsare not evident after a duration of time (e.g. 4 minutes), surmised tobe absorbed by the cured coating composition.

In favored embodiments described herein, the cured coating maintains itsproperties and in particular the property of exhibiting reducedfingerprint visibility after aging for 500 hours at 80° C. In someembodiments, the ratio may increase. However, the ratio is still lessthan 0.80, or 0.70, or 0.60, or 0.50.

The silicone group or fluorinated group of the additive generally lowersthe surface energy of the coating composition and thus may becharacterized as a low surface energy group.

The cured surface layer and coated articles may exhibit “ink repellency”when ink from a pen, commercially available under the trade designation“Sharpie”, beads up into discrete droplets and can be easily removed bywiping the exposed surface with tissues or paper towels, such as tissuesavailable from the Kimberly Clark Corporation, Roswell, Ga. under thetrade designation “SURPASS FACIAL TISSUE.”

A surface comprising the cured coating described herein preferablyexhibits a high advancing contact angle with water of at least 70degrees. More preferably, the advancing contact angle with water is atleast 80 degrees and more preferably at least 90 degrees. Cured coatingcompositions described herein can exhibit high advancing contact angleswith water. The surface comprising the cured coating described hereinpreferably exhibits a receding contact angle with hexadecane of at least40, 45 or 50 degrees and typically no greater than 60 degrees.

The additive will be described herein with respect to monomerscomprising at least one (meth)acrylate group. However, it is appreciatedthat other (meth)acryl, free-radically polymerizable, and ethylenicallyunsaturated functional groups (i.e. polymerizable carbon-carbon doublebond) could be employed in place of the described (meth)acrylate groups.Free-radically polymerizable groups include for example (meth)acrylgroups such as (meth)acrylamides, —SH, allyl, or vinyl and combinationsthereof.

The additive is generally prepared by polymerizing three or moreethylenically unsaturated monomers wherein at least one of such monomershas a low surface energy (terminal) group, at least one second monomercomprises one or more (e.g. primary) hydroxyl groups, and at least onethird monomer comprises a (terminal) alkyl group that may be ahydrophobic group. The additive also typically comprises the residue ofat least one initiator and chain transfer agent as known in the art.

At least one free-radical initiator is typically utilized for thepreparation of the polyacrylate copolymer additive. Useful free-radicalthermal initiators include, for example, azo, peroxide, persulfate, andredox initiators, and combinations thereof. Useful free-radicalphotoinitiators include, for example, those known as useful in the UVcure of acrylate polymers. In some aspects, the copolymer additive issolution polymerized by use of a thermal initiator and thenphotopolymerized after being combined with the polymerizable resin (e.g.hardcoat).

Although the polymerization method is not particularly limited, theadditive is typically prepared via solution polymerization in a (e.g.non-fluorinated) dilute solution with organic solvent. A single organicsolvent or a blend of solvents can be employed.

The additive is typically prepared in a two-step process that comprisesforming a polymeric intermediate by free-radically polymerizing:

i) at least one low surface energy (silicone, perfluoroalkyl,perfluoropolyether) monomer comprising at least one ethylenicallyunsaturated (e.g. (meth)acrylate) group;

ii) at least one monomer comprising at least one ethylenicallyunsaturated (e.g. (meth)acrylate) group and one or more hydroxyl groups;and

iii) at least one monomer comprising at least one ethylenicallyunsaturated (e.g. (meth)acrylate) group and an alkyl group.

In some embodiments, the monomers of i), ii), and iii) aremonofunctional monomers, having a single ethylenically unsaturated (e.g.(meth)acrylate or thiol) group.

In the two-step method a portion of the hydroxyl groups of ii) aresubsequently reacted to convert a portion of the hydroxyl group to anethylenically unsaturated (e.g. (meth)acrylate) group. For example, thehydroxyl group can be reacted with an isocyanatoalkyl(meth)acrylateconverting the hydroxyl group to a urethane linkage. Alternatively, thehydroxyl group can be reacted with acryloyl chloride or methacrylicanhydride.

The molecular weight of the additive may also be controlled by adding asuitable chain transfer agent. Chain transfer agents can be used topromote chain termination and limit gel formation. Useful chain transferagents include, for example, thiols, and polyhalocarbons. Examples ofcommercially available chain transfer agents include tetrabromomethane,1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanethiol,1-decanethiol, 1-dodecanethiol, 1-octadecyl mercaptan,1-pentadecanethiol, 1-hexadecyl mercaptan, tert-nonyl mercaptan,tert-hexadecyl mercaptan, tert-tetradecyl mercaptan,1H,1H,2H,2H-perfluorohexanethio, and1H,1H,2H,2H-perfluorododecyl-1-thiol; as well as thio terminatedpoly(organosiloxane) (e.g. “KF-2001”). Such chain transfer agents canalso provide the (e.g. hydrophobic) alkyl group of the copolymeradditive and/or the low surface energy group of the copolymer additive.

The copolymer additive reaction product is surmised to comprise amixture of unreacted monomeric starting material, oligomeric species,and polymeric species having each of requisite monomeric units.

When the ethylenically unsaturated groups of the starting monomers are(meth)acrylate groups, the additive comprises a polyacrylate backbone.However, the backbone of the forthcoming polyacrylate units mayalternatively comprise other free-radically polymerized groups, aspreviously described.

The polyacrylate additive comprises at least one low surface energygroup having the general formula:

wherein R_(L) is low surface energy silicone or fluorinated group;Q is a connecting group having a valency of at least 2;X is O, S, or NR⁵, where R⁵ is H or lower alkyl of 1 to 4 carbon atoms,andR⁶ is hydrogen or alkyl having from 1 to 4 carbon atoms (e.g., methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec-butyl).

Q can comprise a bond or a straight chain, branched chain, orcyclic-containing connecting group. Q can include an alkylene, anarylene, an aralkylene, an alkarylene. Q can optionally includeheteroatoms such as 0, N, and S, and combinations thereof. Q can alsooptionally include a heteroatom-containing functional group such ascarbonyl or sulfonyl, and combinations thereof.

When the low surface energy group is a silicone group, the siliconegroup is typically derived from an organosiloxane. Preferredsilicon-containing resins are organopolysiloxanes. Organopolysiloxanesare known in the art and are described for example in U.S. Pat. No.3,159,662 (Ashby); U.S. Pat. No. 3,220,972 (Lamoreauz); U.S. Pat. No.3,410,886 (Joy); U.S. Pat. No. 4,609,574 (Keryk); U.S. Pat. No.5,145,886 (Oxman, et. al); U.S. Pat. No. 4,916,169 (Boardman et. al);and U.S. Pat. No. 7,192,795 (Boardman et. al).

Suitable polyorganosiloxanes include linear, cyclic or branchedorganosiloxanes of the formula:R¹ _(b)[(R² _(a)SiO_((4-a)/2))_(c)]_((3-b))Si—X¹

wherein R¹ is a monovalent, straight-chained, branched or cyclic,unsubstituted or substituted hydrocarbon group containing from 1 to 18carbon atoms; R² is independently a monovalent hydrocarbon group from 2to 10 carbon atoms; X¹ is —(CH₂)_(d)—Y where Y is —OH, —SH, —NH₂, or—NHR³, where d=0-10, and R³ is a lower alkyl or cycloalkyl of 1 to 6carbon atoms; each a is independently 0, 1, 2 or 3; b is 0, 1 or 2; andc is 5 to 300. In some embodiments, R² is methyl.

R¹ is typically an alkyl group such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl,neo-pentyl, tert-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl,2,2,4-trimethylpentyl, n-decyl, n-dodecyl, and n-octadecyl; aromaticgroups such as phenyl or naphthyl; alkaryl groups such as 4-tolyl;aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl; andsubstituted alkyl groups such as 3,3,3-trifluoro-n-propyl,1,1,2,2-tetrahydroperfluoro-n-hexyl, and 3-chloro-n-propyl.

Preferably polyorganosiloxanes are linear organosiloxanes of the formula

wherein R¹, R²; and X¹ are the same as just described and u is 5 to 300.

In some embodiments, the polyacrylate additive composition comprises aunit represented by the formula:

wherein RSi is R¹ _(b)[(R² _(a)SiO_((4-a)/2))_(c)]_((3-b))Si— (asdescribed above),Q is —(CH₂)_(d)— (as described above),X is O, S, NR⁵ where R⁵ is H or a lower alkyl of 1 to 4 carbon atoms,andR⁶ is hydrogen or alkyl having from 1 to 4 carbons.

In some embodiments, the additive composition comprises a thio unitrepresented by the formula:[RSi-Q-S]_(t)—wherein RSi and Q are the same as just described and S is sulfur.

Various fluorinated low surface energy groups are known includingperfluoroalkyl groups and perfluoropolyether groups.

In some embodiments, the additive comprises a perfluoroalkyl group. Theterm “perfluoroalkyl group” includes alkyl groups in which all C—H bondsare replaced by C—F bonds as well as groups in which one hydrogen ispresent replacing a terminal fluorine atom. In some embodiments ofperfluoroalkyl groups, when at least one hydrogen is present, theperfluoroalkyl group includes at least one difluoromethyl group.Suitable perfluoroalkyl groups comprise 3 to 12 (i.e., 3, 4, 5, 6, 7, 8,9, 10, 11, or 12) carbon atoms.

In some embodiments, the polyacrylate additive composition comprises aunit represented by the formula:

wherein Rf¹ is a perfluoroalkyl containing group, X is O, S, or NR⁵,where R⁵ is H or a lower alkyl of 1 to 4 carbon atoms, Q is a connectinggroup having a valency of at least 2 as previously described and R⁶ ishydrogen or alkyl, as previously described.

In some embodiments, each Rf¹ is independently a perfluoroalkyl grouphaving from 3 to 6 (e.g., perfluoro-n-hexyl, perfluoro-n-pentyl,perfluoroisopentyl, perfluoro-n-butyl, perfluoroisobutyl,perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoro-n-propyl, orperfluoroisopropyl). In some embodiments, Rf¹ is perfluorobutyl (e.g.,perfluoro-n-butyl). In some embodiments, Rf¹ is perfluoropropyl (e.g.,perfluoro-n-propyl).

In some embodiments, Q is —SO₂N(R⁶)— wherein n ranges from 2 to 4, andR⁶ is hydrogen or alkyl as previously described. In some embodiments,the R⁶ bonded to the nitrogen atom is methyl or ethyl. In someembodiments, the R⁶ bonded to the carbon atoms of the polyacrylatebackbone is hydrogen or methyl.

In some embodiments, the polyacrylate additive composition comprises asingle terminal perfluoroalkyl moiety such as the formula

In other embodiments, the polyacrylate additive composition comprisesrepeat units comprising terminal perfluoroalkyl moieties, such as thefluorochemical oligomeric units described in

U.S. Pat. No. 6,174,964; incorporated herein by reference. Suchpolyacrylate units can be represented by the following formula:

wherein v is 2 to 10 and w is 0 to 5 and R⁴ is an alkyl group of 1-24carbon atoms (as subsequently described in further detail). Preferablythe ratio of v to w is 2:1 or greater.

In one embodiment, the polyacrylate additive composition comprises unitshaving the formula:

Fluorinated free-radically polymerizable acrylate monomers comprisingperfluoroalkyl groups, and methods for their preparation, are known inthe art; (see, e.g., U.S. Pat. No. 2,803,615 (Albrecht et al.) and U.S.Pat. No. 6,664,354 (Savu et al.), the disclosures of which, relating tofree-radically polymerizable monomers and methods of their preparation,are incorporated herein by reference). Methods described for makingnonafluorobutanesulfonamido group-containing structures can be used tomake heptafluoropropanesulfonamido groups by starting withheptafluoropropanesulfonyl fluoride, which can be made, for example, bythe methods described in Examples 2 and 3 of U.S. Pat. No. 2,732,398(Brice et al.), the disclosure of which is incorporated herein byreference. Methods for making other perfluoroalkyl compounds are known;(see, e.g., EP1311637 B1, published Apr. 5, 2006, and incorporatedherein by reference for the disclosure of the preparation of2,2,3,3,4,4,4-heptafluorobutyl 2-methylacrylate). Perfluoroalkylcompounds are also available from commercial sources (e.g.,3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate from Daikin Chemical Sales,Osaka, Japan and 3,3,4,4,5,5,6,6,6-nonafluorohexyl 2-methylacrylate fromIndofine Chemical Co., Hillsborough, N.J.).

In some embodiments, the additive comprises a perfluoropolyether group.The perfluoropolyether group R_(f) can be linear, branched, cyclic, orcombinations thereof and can be saturated or unsaturated. Theperfluoropolyether has at least two catenated oxygen heteroatoms.Exemplary perfluoropolyethers include, but are not limited to, thosethat have perfluorinated repeating units selected from the group of—(C_(p)F_(2p))—, —(C_(p)F_(2p)O)—, —(CF(Z))—, —(CF(Z)O)—,—(CF(Z)C_(p)F_(2p)O)—, —(C_(p)F_(2p)CF(Z)O)—, —(CF₂CF(Z)O)—, orcombinations thereof. In these repeating units, p is typically aninteger of 1 to 10. In some embodiments, p is an integer of 1 to 8, 1 to6, 1 to 4, or 1 to 3. The group Z is a perfluoroalkyl group,perfluoroether group, perfluoropolyether, or a perfluoroalkoxy group,all of which can be linear, branched, or cyclic. The Z group typicallyhas no more than 12 carbon atoms, no more than 10 carbon atoms, or nomore than 9 carbon atoms, no more than 4 carbon atoms, no more than 3carbon atoms, no more than 2 carbon atoms, or no more than 1 carbonatom. In some embodiments, the Z group can have no more than 4, no morethan 3, no more than 2, no more than 1, or no oxygen atoms. In theseperfluoropolyether structures, the different repeat units can bedistributed randomly along the chain.

R_(f) can be monovalent or divalent. In some compounds where R_(f) ismonovalent, the terminal groups can be (C_(p)F_(2p+1))—,(C_(p)F_(2p+1)O)—, (X′C_(p)F_(2p)O)—, or (X′C_(p)F_(2p+1))— where X′ ishydrogen, chlorine, or bromine and p is an integer of 1 to 10. In someembodiments of monovalent R_(f) groups, the terminal group isperfluorinated and p is an integer of 1 to 10, 1 to 8, 1 to 6, 1 to 4,or 1 to 3. Exemplary monovalent R_(f) groups includeCF₃O(C₂F₄O)_(n)CF₂—, C₃F₇O(CF₂CF₂CF₂O)_(n)CF₂CF₂—, andC₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)— wherein n has an average value of 0 to50, 1 to 50, 3 to 30, 3 to 15, or 3 to 10.

Suitable structures for divalent R_(f) groups include, but are notlimited to, —CF₂O(CF₂O)_(q)(C₂F₄O)_(n)CF₂—, —(CF₂)₃O(C₄F₈O)_(n)(CF₂)₃—,—CF₂O(C₂F₄O)_(n)CF₂—, —CF₂CF₂O(CF₂CF₂CF₂O)_(n)CF₂CF₂—, and—CF(CF₃)(OCF₂CF(CF₃))_(s)OC_(t)F_(2t)O(CF(CF₃)CF₂O)_(n)CF(CF₃)—, whereinq has an average value of 0 to 50, 1 to 50, 3 to 30, 3 to 15, or 3 to10; n has an average value of 0 to 50, 3 to 30, 3 to 15, or 3 to 10; shas an average value of 0 to 50, 1 to 50, 3 to 30, 3 to 15, or 3 to 10;the sum (n+s) has an average value of 0 to 50 or 4 to 40; the sum (q+n)is greater than 0; and t is an integer of 2 to 6.

For embodiments wherein Rf is divalent and two (e.g. terminal) reactivegroups are bonded to Rf (such as in the case of a diol), theconcentration of such divalent monomer is sufficiently low as to avoidexcessive crosslinking that can result in formation of a gel.

In some embodiments, the polyacrylate additive composition comprises aunit represented by the following formula:

wherein Rf is a (e.g. monovalent) perfluoropolyether group and Q, X andR⁶ are the same as previously described.

Free-radically polymerizable acrylate monomers comprisingperfluoropolyether groups, and methods for their preparation, are knownin the art. The perfluoropolyether (meth)acrylate compounds can besynthesized by known techniques such as described in U.S. Pat. Nos.3,553,179 and 3,544,537 as well as U.S. Patent Application PublicationNo. US2004/0077775, published Apr. 22, 2004, “Fluorochemical CompositionComprising a Fluorinated Polymer and Treatment of a Fibrous SubstrateTherewith”. Suitable perfluoropolyether (meth)acrylate compounds includefor example

HFPO—C(O) NHCH₂CH₂OC(O)CH═CH₂, HFPO—

C(O)NHCH₂CH₂OCH₂CH₂OCH₂CH₂OC(O)CH═CH₂,

HFPO—C(O)NH—(CH₂)₆OC(O)CH═CH₂ and various other perfluoropolyethercompounds such as described in U.S. Publication No. US2005/0250921 andU.S. Publication No. US2005/0249940; incorporated by reference.(Meth)acrylate copolymers comprising perfluoropolyether moieties andtheir preparations are known in the art. See WO2009/076389, Qiu et. al.These preparations may employ chain transfer agents such as thiols, andthermal initiators such as peroxides and azo compounds.

In some embodiments, Rf is HFPO—. Unless otherwise noted, “HFPO—” refersto the end group F(CF(CF₃)CF₂O)_(a)CF(CF₃)— of the methyl esterF(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)OCH₃, wherein “a” averages 2 to 15. In someembodiments, “a” averages between 3 and 10 or “a” averages between 5 and8. Such species generally exist as a distribution or mixture ofoligomers with a range of values for “a”, so that the average value of amay be non-integer. For example, in one embodiment, “a” averages 6.2.The molecular weight of the HFPO— perfluoropolyether material variesdepending on the number “a” of repeat units from about 940 g/mole toabout 1600 g/mole, with 1100 g/mole to 1400 g/mole typically beingpreferred.

The polyacrylate additive composition further comprises a unit havinghydroxyl groups represented by the following formula:

R_(OH) is a hydroxyl containing group;Q is a connecting group having a valency of at least 2 as previouslydescribed;X is O, S, or NR⁵, where R⁵ is H or lower alkyl of 1 to 4 carbon atoms;andR⁶ is hydrogen or alkyl as previously described.

The hydroxyl containing group R_(OH) can contain one or more hydroxylgroups. In some embodiments, the unit comprises a single primaryhydroxyl group (i.e. —CH₂OH). In other embodiments, the unit comprises aprimary hydroxy group and one or more secondary hydroxyl groups (i.e.R′R″CHOH where R′, R″, are divalent (e.g. alkylene, ether, or ester)groups.

In some embodiments, the units comprising R_(OH) do not comprise anethylene oxide or propylene oxide repeat unit between the polyacrylatebackbone and hydroxyl groups.

In the synthesis of the copolymer additive, a portion of the hydroxylgroups are converted to free-radically polymerizable (e.g.(meth)acrylate) groups such as by the reaction with isocyanatoalkylacrylate. However, a portion of the hydroxyl groups remain present inthe additive.

The portion of the hydroxyl groups that are reacted result in thepolyacrylate additive composition further comprising units representedby the following formula:

whereinA is a (meth)acryl functional group such as —OC(O)C(R2)═CH2, where R2 isa lower alkyl of 1 to 4 carbon atoms or H or F;a ranges from 1 to 6; andR_(OH1) is the residue of the R_(OH) group (i.e. after functionalizationwith (meth)acryl functionality);andQ and X are the same as just previously described with respect to theunit comprising hydroxyl groups.

In some embodiments, a is 1.

The polyacrylate additive composition further comprises a unitrepresented by the following formula:

wherein Q and X are the same as just previously described and R⁴ is analkyl group of 1-24 carbon atoms. R⁴ may be a straight-chain, branched,or contain cycloalkyl moieties. In some embodiments, R⁴ is a lower alkylgroup comprising at least 1, 2, 3, or 4 carbon atoms (such as describedfor R⁶). In other embodiments R⁴ is a hydrophobic alkyl group comprisingat least 6, 7, or 8 carbon atoms. In yet other embodiments, R⁴ is afatty alkyl group having at least 12, or 14, or 15, or 18 carbon atoms.

In some embodiments, the polyacrylate additive comprises other optionalunits such as a unit represented by the following formula:

wherein R is a hydrophobic group, such as an alkyl or alkenyl grouphaving greater than 6, 7, or 8 carbon atoms, as previously described;Ra is independently an alkylene group C_(x)H_(2x) where x=2 to 4, inwhich C_(x)H_(2x) may be straight chain or branched or a combination ofthe two;j is the number of alkylene oxide repeat units and ranges from 1 to 50;andR⁶ is hydrogen or alkyl as previously described.

In some embodiments, j ranges from 2 to 25. Such group comprisingalkylene oxide repeat units may be derived from a non-ionic surfactant.For example, a non-ionic surfactant comprising a (meth)acrylate groupcan be formed by reacting the hydroxyl group of the previously describedfatty alcohols and derivatives thereof with a (meth)acrylic acid or a(meth)acryloyl halide, or functional (meth)acrylate compound such as anisocyanato-functional (meth)acrylate compound. Such (meth)acrylatefunctional surfactant can then be copolymerized with the other(meth)acrylate compounds.

When the additive comprises greater than 6 repeat units of ethyleneoxide, such additive may have improved compatibility with hydroxyl groupcontaining solvents, commonly known as alcohols. Alcohol based coatingcompositions are especially useful for coating light transmissivesubstrates such as polycarbonate, acrylic, cellulose acetate, andcellulose triacetate which are susceptible to swelling, cracking, orcrazing by organic solvents such as ketones (e.g. MEK), aromaticsolvents (e.g. toluene), and esters (e.g. acetate solvents).

The additive may be represented by the general formula:-[M^(L)]_(l)-[M^(OH)]_(q)-[M^(A)]_(p)-[M^(R4)]_(o)—wherein[M^(L)] represent units derived from one or more ethylenicallyunsaturated monomers comprising a low surface energy silicone offlurorinated group;[M^(OH)] represent units derived from one or more ethylenicallyunsaturated monomers and at least one hydroxyl group;[M^(A)] represent units comprising a residue of [M^(OH)] and afree-radically polymerizable group; and[M^(R4]) represent units derived from one or more ethylenicallyunsaturated monomers comprising an alkyl group.

In some embodiments, the additive may be represented by the generalformula:-[M^(L)]_(l)[M^(OH)]_(q)-[M^(A)]_(p)-[M^(R4]) _(o)-[M^(AO)]_(n)—wherein [M^(L)], [M^(OH)], [M^(A)], [M^(R4)] are the same as justdescribed and [M^(AO)] represents units derived from one ore moreethylenically unsaturated monomers having alkylene oxide repeat units.

The polyacrylate additive comprises a combination of at least thefollowing four units:

In some embodiments, the polyacrylate additive comprises a combinationof the four units just described and the following previously describedfifth unit:

The unit comprising the low surface energy group [M^(L)] or (R_(L)) maybe any one or combination of units comprising silicone groups,perfluroralkyl groups, perflurorpolyether groups, or mixture thereof aspreviously described.

The number of each of the respective units of the polyacrylate additivecan vary. For example, l, q, p, o may independently range from 1 to 100;whereas n can range from 0 to 100.

The number of 1 units (i.e. units comprising the low surface energygroup) are chosen such that the copolymer additive comprises about 5-50%by weight 1 units, more preferably about 10-40% by weight 1 units. Thenumber of 1 units is equal to the sum of r (i.e. units comprisingsilicone group RSi), s (i.e. units comprising perfluoroalkyl containinggroup Rf¹), and m (i.e. units comprising perflurorpolyether group Rf).The polyacrylate additive may further comprise low surface energy groupsderived from a chain transfer unit. The number of 1 units of [M^(L)] isequal to the sum of r, s, m, and t.

The number of q units (i.e. units comprising at least one hydroxylgroup) are chosen such that the OH EW of the copolymer additive rangesfrom about 200 g/equivalent hydroxyl group to 2000 g/equivalent hydroxylgroups, and more preferably 250 g/equivalent OH to 750. On a weightpercentage basis this is a range of about 10 to 50% by weight q units.(The copolymer intermediate, prior to converting a portion of thehydroxyl groups to free-radically polymerizable group has a higherhydroxyl content than the copolymer additive.)

The number of p units (i.e. units comprising at least one free-radicallypolymerizable group) which are derived from the q units, are chosen suchthat the copolymer additive comprises about 1 to 20% by weight p units,and more preferably 1.5 to 10% by weight p units.

The number of o units (i.e. units comprising an alkyl group) are chosensuch that the copolymer additive comprises about 5-80% by weight ounits, and more preferably 20-70% by weight o units. The polyacrylateadditive may further comprise alkyl groups derived from a chain transferunit. The number of o units of [M^(R4)] is equal to the sum of o and anyalkyl units derived from a chain transfer agent.

The number of optional n units (i.e. units comprising alkylene oxiderepeat units and a hydrophobic group) are chosen such that the copolymeradditive comprises about 0-50% by weight o units, and more preferably10-50% by weight o units.

The non-ionic surfactant and additive are typically dispersed in ahardcoat composition in combination with a (e.g. alcohol based) solvent,applied to a surface or substrate, such as an optical substrate andphotocured. The hardcoat is a tough, abrasion resistant layer thatprotects the optical substrate and the underlying display screen fromdamage from causes such as scratches, abrasion and solvents. Typicallythe hardcoat is formed by coating a curable liquid ceramer compositiononto the substrate and curing the composition in situ to form a hardenedfilm.

The coating composition described herein can be employed as a one-layerhardcoat composition. For embodiments wherein high durability isdesired, the hardcoat composition typically further comprises (e.g.surface modified) inorganic particles, such as silica. The thickness ofthe hardcoat surface layer is typically at least 0.5 microns, preferablyat least 5 micron, and more preferably at least 10 microns. Thethickness of the hardcoat layer is generally no greater than 25 microns.Preferably the thickness ranges from 5 microns to 20 microns.

Alternatively, the coating composition may be free of inorganic oxidesparticles for uses where durability is not required. In yet otherembodiments, an inorganic particle free surface layer may be provided incombination with an inorganic particle containing hardcoat layerdisposed between the substrate and the surface layer. This will bereferred to as a two-layer hardcoat. In these embodiments, the surfacelayer preferably has a thickness ranging from about 1 to 10 microns.

The coating compositions described herein are sufficiently durable suchthat the cured coating exhibits no evidence of scratching or only a fewscratches (e.g. 1-3) when tested according to the steel wool abrasionresistance test method described in WO2009/076389 and the forthcomingexamples using a weight of 300 g and 10 wipes.

A variety of binder precursors that form a crosslinked polymeric matrixupon curing can be employed in the hardcoat.

Di(meth)acryl binder precursors include for example 1,3-butylene glycoldiacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,1,6-hexanediol monoacrylate monomethacrylate, ethylene glycoldiacrylate, alkoxylated aliphatic diacrylate, alkoxylated cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylatedneopentyl glycol diacrylate, caprolactone modified neopentylglycolhydroxypivalate diacrylate, caprolactone modified neopentylglycolhydroxypivalate diacrylate, cyclohexanedimethanol diacrylate, diethyleneglycol diacrylate, dipropylene glycol diacrylate, ethoxylated bisphenolA diacrylate, hydroxypivalaldehyde modified trimethylolpropanediacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate,propoxylated neopentyl glycol diacrylate, tetraethylene glycoldiacrylate, tricyclodecanedimethanol diacrylate, triethylene glycoldiacrylate, tripropylene glycol diacrylate.

Tri(meth)acryl binder precursor include for example glyceroltriacrylate, trimethylolpropane triacrylate, ethoxylatedtrimethylolpropane triacrylates (e.g. having 3 to 20 ethoxylate repeat),propoxylated glycerol triacrylates, trimethylolpropane triacrylate,tris(2-hydroxyethyl)isocyanurate triacrylate. Higher functionality(meth)acryl containing compounds include for exampleditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate,ethoxylated pentaerythritol tetraacrylate, caprolactone modifieddipentaerythritol hexaacrylate.

One commercially available form of pentaerythritol triacrylate (“PET3A”)is SR444C and one commercially available form of pentaerythritoltetraacrylate (“PET4A”) is SR295, each available from Sartomer Companyof Exton, Pa.

Oligomeric (meth)acryl such as urethane acrylates, polyester acrylates,epoxy acrylates; and polyacrylamide analogues of the foregoing can alsobe employed as the binder.

In one embodiment, the binder may comprise one or more N,N-disubstitutedacrylamide and or N-substituted-N-vinyl-amide monomers as described inBilkadi et al. The hardcoat may be derived from a ceramer compositioncontaining about 20 to about 80% ethylenically unsaturated monomers andabout 5 to about 40% N,N-disubstituted acrylamide monomer orN-substituted-N-vinyl-amide monomer, based on the total weight of thesolids in the ceramer composition.

To facilitate curing, polymerizable compositions described herein mayfurther comprise at least one free-radical thermal initiator and/orphotoinitiator. Typically, such an initiator and/or photoinitiator arepresent in an amount less than about 10 percent by weight, moretypically less than about 5 percent of the polymerizable composition,based on the total weight of the polymerizable composition. Free-radicalcuring techniques are well known in the art and include, for example,thermal curing methods as well as radiation curing methods such aselectron beam or ultraviolet radiation. Further details concerning freeradical thermal and photopolymerization techniques may be found in, forexample, U.S. Pat. No. 4,654,233 (Grant et al.); U.S. Pat. No. 4,855,184(Klun et al.); and U.S. Pat. No. 6,224,949 (Wright et al.).

Useful free-radical thermal initiators include, for example, azo,peroxide, persulfate, and redox initiators, and combinations thereof.

Useful free-radical photoinitiators include, for example, those known asuseful in the UV cure of acrylate polymers such as described inWO2006/102383.

The polymerizable composition for use as the surface layer or anunderlying hardcoat layer preferably contains surface modified inorganicparticles that add mechanical strength and durability to the resultantcoating.

A variety of inorganic oxide particles can be used in the hardcoat. Theinorganic oxide particles can consist essentially of or consist of asingle oxide such as silica, or can comprise a combination of oxides,such as silica and aluminum oxide, or a core of an oxide of one type (ora core of a material other than a metal oxide) on which is deposited anoxide of another type. Silica is a common inorganic particle. Theinorganic oxide particles are often provided in the form of a solcontaining a colloidal dispersion of inorganic oxide particles in liquidmedia. The sol can be prepared using a variety of techniques and in avariety of forms including hydrosols (where water serves as the liquidmedium), organosols (where organic liquids so serve), and mixed sols(where the liquid medium contains both water and an organic liquid),e.g., as described in U.S. Pat. No. 5,648,407 (Goetz et al.); U.S. Pat.No. 5,677,050 (Bilkadi et al.) and U.S. Pat. No. 6,299,799 (Craig etal.). Aqueous sols (e.g. of amorphous silica) can be employed. Solsgenerally contain at least 2 wt-%, at least 10 wt-%, at least 15 wt-%,at least 25 wt-%, and often at least 35 wt-% colloidal inorganic oxideparticles based on the total weight of the sol. The amount of colloidalinorganic oxide particle is typically no more than 50 wt-% (e.g. 45wt-%). The surface of the inorganic particles can be “acrylatefunctionalized” as described in Bilkadi et al. The sols can also bematched to the pH of the binder, and can contain counter ions orwater-soluble compounds (e.g., sodium aluminate), all as described inKang et al. '798.

Various high refractive index inorganic oxide particles can be employedsuch as for example zirconia (“ZrO₂”), titania (“TiO₂”), antimonyoxides, alumina, tin oxides, alone or in combination. Mixed metal oxidesmay also be employed. Zirconias for use in the high refractive indexlayer are available from Nalco Chemical Co. under the trade designation“Nalco OOSSOO8” and from Buhler AG Uzwil, Switzerland under the tradedesignation “Buhler zirconia Z—WO sol”. Zirconia nanoparticle can alsobe prepared such as described in U.S. Pat. Nos. 7,241,437 and 6,376,590.

The inorganic nanoparticles are preferably treated with a surfacetreatment agent. Surface-treating the nano-sized particles can provide astable dispersion in the polymeric resin. Preferably, thesurface-treatment stabilizes the nanoparticles so that the particleswill be well dispersed in the polymerizable resin and results in asubstantially homogeneous composition. Furthermore, the nanoparticlescan be modified over at least a portion of its surface with a surfacetreatment agent so that the stabilized particle can copolymerize orreact with the polymerizable resin during curing. The incorporation ofsurface modified inorganic particles is amenable to covalent bonding ofthe particles to the free-radically polymerizable organic components,thereby providing a tougher and more homogeneous polymer/particlenetwork.

In general, a surface treatment agent has a first end that will attachto the particle surface (covalently, ionically or through strongphysisorption) and a second end that imparts compatibility of theparticle with the resin and/or reacts with resin during curing. Examplesof surface treatment agents include alcohols, amines, carboxylic acids,sulfonic acids, phosphonic acids, silanes and titanates. The preferredtype of treatment agent is determined, in part, by the chemical natureof the metal oxide surface. Silanes are preferred for silica and otherfor siliceous fillers. Silanes and carboxylic acids are preferred formetal oxides such as zirconia. The surface modification can be doneeither subsequent to mixing with the monomers or after mixing. It ispreferred in the case of silanes to react the silanes with the particleor nanoparticle surface before incorporation into the resin. Therequired amount of surface modifier is dependant upon several factorssuch as particle size, particle type, modifier molecular wt, andmodifier type. In general, it is preferred that approximately amonolayer of modifier is attached to the surface of the particle. Theattachment procedure or reaction conditions required also depend on thesurface modifier used. For silanes it is preferred to surface treat atelevated temperatures under acidic or basic conditions for from 1-24 hrapproximately. Surface treatment agents such as carboxylic acids may notrequire elevated temperatures or extended time.

Representative embodiments of surface treatment agents suitable for thecompositions include compounds such as, for example, isooctyltrimethoxy-silane, N-(3-triethoxysilylpropyl) methoxyethoxyethoxyethylcarbamate, N-(3-triethoxysilylpropyl) methoxyethoxyethoxyethylcarbamate, 3-(methacryloyloxy)propyltrimethoxysilane,3-acryloxypropyltrimethoxysilane,3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(acryloyloxypropyl)methyldimethoxysilane,3-(methacryloyloxy)propyldimethylethoxysilane, 3-(methacryloyloxy)propyldimethylethoxysilane, vinyldimethylethoxysilane,phenyltrimethoxysilane, n-octyltrimethoxysilane,dodecyltrimethoxysilane, octadecyltrimethoxysilane,propyltrimethoxysilane, hexyltrimethoxysilane,vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane,vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane,vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-t-butoxysilane,vinyltris-isobutoxysilane, vinyltriisopropenoxysilane,vinyltris(2-methoxyethoxy)silane, styrylethyltrimethoxysilane,mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane,acrylic acid, methacrylic acid, oleic acid, stearic acid, dodecanoicacid, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MEEAA),beta-carboxyethylacrylate (BCEA), 2-(2-methoxyethoxy)acetic acid,methoxyphenyl acetic acid, and mixtures thereof.

The surface modification of the particles in the colloidal dispersioncan be accomplished in a variety of known ways, such as described inU.S. Pat. Nos. 7,241,437 and 6,376,590.

A combination of surface modifying agents can be useful, wherein atleast one of the agents has a functional group co-polymerizable with ahardenable resin. Combinations of surface modifying agent can result inlower viscosity. For example, the polymerizing group can beethylenically unsaturated or a cyclic function subject to ring openingpolymerization. An ethylenically unsaturated polymerizing group can be,for example, an acrylate or methacrylate, or vinyl group. A cyclicfunctional group subject to ring opening polymerization generallycontains a heteroatom such as oxygen, sulfur or nitrogen, and preferablya 3-membered ring containing oxygen such as an epoxide.

A preferred combination of surface modifying agent includes at least onesurface modifying agent having a functional group that iscopolymerizable with the organic component of the polymerizable resinand a second amphiphilic modifying agent, such as a polyether silane,that may act as a dispersant. The second modifying agent is preferably apolyalkyleneoxide containing modifying agent that is optionallyco-polymerizable with the organic component of the polymerizablecomposition.

The inorganic particles preferably have a substantially monodispersesize distribution or a polymodal distribution obtained by blending twoor more substantially monodisperse distributions. Alternatively, theinorganic particles can be introduced having a range of particle sizesobtained by grinding the particles to a desired size range. Theinorganic oxide particles are typically non-aggregated (substantiallydiscrete), as aggregation can result in optical scattering (haze) orprecipitation of the inorganic oxide particles or gelation. Theinorganic oxide particles are typically colloidal in size, having anaverage particle diameter of 5 nanometers to 100 nanometers. Theparticle size of the high index inorganic particles is preferably lessthan about 50 nm in order to provide sufficiently transparenthigh-refractive index coatings. The average particle size of theinorganic oxide particles can be measured using transmission electronmicroscopy to count the number of inorganic oxide particles of a givendiameter.

The coating composition described herein can be used to form a (e.g.cured) surface layer, a coated article, or a coated surface such as byapplying the coating composition to a surface (e.g. of a substrate orarticle) and curing polymerizable components of the coating composition.Once polymerizable components present in the coating composition havebeen cured, a suitable solvent (such as hexane in some embodiments) canbe used to extract the lipophilic liquid, such as the unpolymerizablesurfactant, from the coated surface or cured coating composition.

The coated surface typically comprises a polymeric organic materialcomprising a plurality of pores. Although the cured coating composition(i.e. surface layer) may comprise nano-sized pores (e.g. less than 200,or 100, or 50 nanometers), the cured coating is typically free of poresof 1 micron or greater. In some embodiments, the average diameter of thepores is at least 10, 15, or 20 nanometers.

A portion of the pores are interconnected, forming a network (e.g. oftunnels). The lipophilic liquid (e.g. unpolymerizable surfactant) ispresent in the pores of the polymeric organic material. Withoutintending to be bound by theory, it is surmised that the wt-% ofextractable lipophilic liquid (e.g. unpolymerizable surfactant) relatesto the extent of interconnectivity of the pores, as well as theconcentration of lipophilic liquid (e.g. unpolymerizable surfactant)present in the coating of the coated surface. It has been found thatwhen a coating composition comprises a low amount of unpolymerizablesurfactant (e.g. about 3 wt-%), the amount of lipophilic extractablematerial relative to the total weight of the coating composition is lessthan 0.02 wt-%. At this relatively low concentration of free lipophilicliquid (i.e. not covalently bonded to the polymeric organic material),the lipophilic liquid is surmised to be evenly distributed throughoutthe coated surface. Although a small portion of the lipophilic liquid isexposed at the outermost surface, the majority of the lipophilic liquidis within the cured coating beneath the exposed surface, resulting inonly a fraction of the total amount of lipophilic liquid beingextractable.

However, when the coating composition comprises greater amounts oflipophilic liquid (e.g. unpolymerizable surfactant) the (i.e. cured)coating composition comprises at least 0.5, 1, 2, 3, 4, or 5 wt-% ofsolvent extractable lipophilic material. The concentration of materialthat can be solvent extracted from the coated surface is typically nogreater than 15 wt-% and in favored embodiments, no greater than 10wt-%.

As the concentration of lipophilic liquid (e.g. unpolymerizablesurfactant) increases, the number and/or size of the pores increase suchthat a network of interconnected pores is formed. This may be caused bynanoscopic phase separation of the lipophilic liquid (e.g.unpolymerizable surfactant) from the polymerized resin. If all thelipophilic liquid (e.g. unpolymerizable surfactant) was accessible forextraction, then all the lipophilic liquid would be present in poresexposed to the surface as isolated pores, interconnected pores, or acombination thereof. Thus, 100% of the total pores are present asisolated pores, interconnected pores, or a combination thereof.Typically, less than all the lipophilic liquid (e.g. unpolymerizablesurfactant) is solvent extractable from the coated surface. For example,in some embodiments, typically no greater than 90 wt-% or 95 wt-% of thetotal lipophilic liquid (e.g. unpolymerizable surfactant) is solventextractable from the cured coating. Thus, 5 or 10% of the lipophilicliquid-containing pores are unexposed to the surface as buried pores. Insome embodiments, at least 10, 15, 20, 25, 30, 35, 40, 45, or 50% of thelipophilic liquid-containing pores are exposed to the surface asisolated pores, interconnected pores, or a combination thereof. Further,the lipophilic liquid-containing pores exposed to the surface asisolated pores, interconnected pores, or a combination thereof, mayrange up to 75, 80, 85, or 90%.

The pore volume of a (e.g. cured) coating or coated (e.g. film) surfacecan be determined using various techniques in the art. One techniquedeveloped by Brunauer, Emmett and Teller, see S. Brunauer, “PhysicalAdsorption” (Princeton University Press, Princeton, N.J., 1945, iscommonly referred to as “BET” gas adsorption. In some embodiments, thecoated surface described herein comprises a plurality of pores having apore volume of at least 0.01 cc/g, or 0.02 cc/g. In some embodiments,the pore volume is no greater than 0.15 cc/g, or no greater than 0.10cc/g, or no greater than 0.09 cc/g, or no greater than 0.08 cc/g, or nogreater than 0.07 cc/g. BET gas adsorption can also be used to determinethe surface area of a surface. In some embodiments, the surface area ofthe coated surface described herein is at least 1 m²/g, or 5 m²/g, or 10m²/g. The surface area is typically no greater than 50 m²/g, or 45 m²/g,or 40 m²/g, or 35 m²/g, or 30 m²/g.

In some embodiments, a gas adsorption isotherm of the coated surface hasa Type H2 hysteresis loop, as described in the IUPAC publication“Reporting Physisorption Data for Gas/Solid Systems with SpecialReference to the Determination of Surface Area and Porosity”, Pure &Applied Chemistry, Volume 57, No. 4, pp. 603-619, 1985. A Type H2hysteresis loop is characteristic of a system of disordered pores (i.e.random spatial arrangement of the pores) in a network of interconnectedpores with some pore blocking (i.e. necking or small diameter passagesbetween pores that provide some resistance to flow betweeninterconnected pores.

The optical film having a surface layer of the cured coating asdescribed herein may have a gloss or matte surface. Matte filmstypically have lower transmission and higher haze values than typicalgloss films. Whereas gloss surfaces typically have a gloss of at least130 as measured according to ASTM D 2457-03 at 60°; matte surfaces havea gloss of less than 120. In some embodiments, the haze is less than 5%,or 2.5%, or 1% depending on the intended end use as measured accordingto ASTM D1003.

A particulate matting agent can be incorporated into the polymerizablecomposition in order to impart anti-glare properties to the surfacelayer as described in WO 2008/067262. The particulate matting agent canprevent uneven coloration caused by interference with an associated hardcoat layer. One commercially available silica particulate matting agenthaving an average particle size of 3.5 microns is commercially availablefrom W.R. Grace and Co., Columbia, Md. under the trade designation“Syloid C803”.

The coating composition may optionally comprise an antistatic agent asdescribed in WO 2008/067262. Various antistatic particles arecommercially available as water-based and solvent-based

The non-ionic surfactant, additive, and hardcoat composition can bedispersed in a solvent to form a dilute coating composition. The amountof solids in the coating composition is typically at least 20 wt-% andusually no greater than about 75 wt-%. For some optical substrate suchas polycarbonate, acrylic, cellulose acetate, and cellulose triacetate,it is preferred to employ an alcohol based solvent including for examplemethanol, ethyl alcohol, isopropyl alcohol, propanol, etc. as well asglycol ethers such as propylene glycol monomethyl ether or ethyleneglycol monomethyl ether, etc. For such optical substrates, the coatingcompositions may contain predominantly alcohol solvent(s). For otheruses, however, alcohol based solvent(s) may be combined with other (i.e.non-alcohol) solvents.

Thin coating layers can be applied to the optical substrate using avariety of techniques, including dip coating, forward and reverse rollcoating, wire wound rod coating, and die coating. Die coaters includeknife coaters, slot coaters, slide coaters, fluid bearing coaters, slidecurtain coaters, drop die curtain coaters, and extrusion coaters amongothers. Many types of die coaters are described in the literature suchas by Edward Cohen and Edgar Gutoff, Modern Coating and DryingTechnology, VCH Publishers, N Y 1992, ISBN 3-527-28246-7 and Gutoff andCohen, Coating and Drying Defects: Troubleshooting Operating Problems,Wiley Interscience, NY ISBN 0-471-59810-0.

A die coater generally refers to an apparatus that utilizes a first dieblock and a second die block to form a manifold cavity and a die slot.The coating fluid, under pressure, flows through the manifold cavity andout the coating slot to form a ribbon of coating material. Coatings canbe applied as a single layer or as two or more superimposed layers.Although it is usually convenient for the substrate to be in the form ofa continuous web, the substrate may also be a succession of discretesheets.

Any surface that is routinely touched could benefit from the coatingcomposition described herein. Examples include optical displays (e.g.,television screens, computer screens, cell phone screens, consoledisplays in automobiles), optical films (e.g., screen protectors,privacy films), automobile windows, consumer appliances (e.g., stovetop, outer surfaces of refrigerator), etc.

The term “optical display”, or “display panel”, can refer to anyconventional optical displays, including but not limited tomulti-character multi-line displays such as liquid crystal displays(“LCDs”), plasma displays, front and rear projection displays, cathoderay tubes (“CRTs”), and signage, as well as single-character or binarydisplays such as light emitting diodes (“LEDs”), signal lamps, andswitches. The exposed surface of such display panels may be referred toas a “lens.” The invention is particularly useful for displays having aviewing surface that is susceptible to being touched or contacted by inkpens, markers and other marking devices, wiping cloths, paper items andthe like.

The coatings of the invention can be employed in a variety of portableand non-portable information display articles. These articles includePDAs, cell phones (including combination PDA/cell phones), LCDtelevisions (direct lit and edge lit), touch sensitive screens, wristwatches, car navigation systems, global positioning systems, depthfinders, calculators, electronic books, CD and DVD players, projectiontelevision screens, computer monitors, notebook computer displays,instrument gauges, instrument panel covers, signage such as graphicdisplays and the like. The viewing surfaces can have any conventionalsize and shape and can be planar or non-planar, although flat paneldisplays are preferred. The coating composition or coated film, can beemployed on a variety of other articles as well such as for examplecamera lenses, eyeglass lenses, binocular lenses, mirrors,retroreflective sheeting, automobile windows, building windows, trainwindows, boat windows, aircraft windows, vehicle headlamps andtaillights, display cases, road pavement markers (e.g. raised) andpavement marking tapes, overhead projectors, stereo cabinet doors,stereo covers, watch covers, as well as optical and magneto-opticalrecording disks, and the like.

A variety of substrates can be utilized in the articles of theinvention. Suitable substrate materials include glass as well asthermosetting or thermoplastic polymers such as polycarbonate,poly(meth)acrylate (e.g., polymethyl methacrylate or “PMMA”),polyolefins (e.g., polypropylene or “PP”), polyurethane, polyesters(e.g., polyethylene terephthalate or “PET”), polyamides, polyimides,phenolic resins, cellulose diacetate, cellulose triacetate, polystyrene,styrene-acrylonitrile copolymers, epoxies, and the like. Such substratesare typically non-absorbent with respect to both aqueous solutions andoils.

Typically the substrate will be chosen based in part on the desiredoptical and mechanical properties for the intended use. Such mechanicalproperties typically will include flexibility, dimensional stability andimpact resistance. The substrate thickness typically also will depend onthe intended use. For most applications, a substrate thickness of lessthan about 0.5 mm is preferred, and is more preferably about 0.02 toabout 0.2 mm. Self-supporting polymeric films are preferred. Films madefrom polyesters such as PET or polyolefins such as PP (polypropylene),PE (polyethylene) and PVC (polyvinyl chloride) are particularlypreferred. The polymeric material can be formed into a film usingconventional filmmaking techniques such as by extrusion and optionaluniaxial or biaxial orientation of the extruded film. The substrate canbe treated to improve adhesion between the substrate and the hardcoatlayer, e.g., chemical treatment, corona treatment such as air ornitrogen corona, plasma, flame, or actinic radiation. If desired, anoptional tie layer or primer can be applied to the substrate and/orhardcoat layer to increase the interlayer adhesion.

Various light transmissive optical films are known including but notlimited to, multilayer optical films, microstructured films such asretroreflective sheeting and brightness enhancing films, (e.g.reflective or absorbing) polarizing films, diffusive films, as well as(e.g. biaxial) retarder films and compensator films such as described inU.S. Patent Application Publication No. 2004/0184150.

As described is U.S. Patent Application Publication 2003/0217806,multilayer optical films provide desirable transmission and/orreflection properties at least partially by an arrangement ofmicrolayers of differing refractive index. The microlayers havedifferent refractive index characteristics so that some light isreflected at interfaces between adjacent microlayers. The microlayersare sufficiently thin so that light reflected at a plurality of theinterfaces undergoes constructive or destructive interference in orderto give the film body the desired reflective or transmissive properties.For optical films designed to reflect light at ultraviolet, visible, ornear-infrared wavelengths, each microlayer generally has an opticalthickness (i.e., a physical thickness multiplied by refractive index) ofless than about 1 μm. However, thicker layers can also be included, suchas skin layers at the outer surfaces of the film, or protective boundarylayers disposed within the film that separate packets of microlayers.Multilayer optical film bodies can also comprise one or more thickadhesive layers to bond two or more sheets of multilayer optical film ina laminate.

Further details concerning multilayer optical films and relatedconstructions can be found in U.S. Pat. No. 5,882,774 (Jonza et al.),and PCT Publications WO95/17303 (Ouderkirk et al.) and WO99/39224(Ouderkirk et al.). Polymeric multilayer optical films and film bodiescan comprise additional layers and coatings selected for their optical,mechanical, and/or chemical properties. See U.S. Pat. No. 6,368,699(Gilbert et al.). The polymeric films and film bodies can also compriseinorganic layers, such as metal or metal oxide coatings or layers.

Various permanent and removable grade adhesive compositions may becoated on the opposite side (i.e. to the hardcoat) of the substrate sothe article can be easily mounted to a display surface. Suitableadhesive compositions include (e.g. hydrogenated) block copolymers suchas those commercially available from Kraton Polymers of Westhollow,Texas under the trade designation “Kraton G-1657”, as well as other(e.g. similar) thermoplastic rubbers. Other exemplary adhesives includeacrylic-based, urethane-based, silicone-based, and epoxy-basedadhesives. Preferred adhesives are of sufficient optical quality andlight stability such that the adhesive does not yellow with time or uponweather exposure so as to degrade the viewing quality of the opticaldisplay. The adhesive can be applied using a variety of known coatingtechniques such as transfer coating, knife coating, spin coating, diecoating and the like. Exemplary adhesives are described in U.S. PatentApplication Publication No. 2003/0012936. Several of such adhesives arecommercially available from 3M Company, St. Paul, Minn. under the tradedesignations 8141, 8142, and 8161.

Glossary

For the following defined terms, these definitions shall be applied,unless a different definition is given in the claims or elsewhere in thespecification.

“Free-radically polymerizable” refers to the ability of monomers,oligomers, polymers or the like to participate in crosslinking reactionsupon exposure to a suitable source of free radicals.

“(Meth)acryl” refers to functional groups including acrylates,methacrylates, acrylamides, methacrylamides, alpha-fluoroacrylates,thioacrylates and thio-methacrylates. A preferred (meth)acryl group isacrylate.

“Monovalent perfluoropolyether moiety” refers to a perfluoropolyetherchain having one end terminated by a perfluoroalkyl group.

Unless otherwise noted, “HFPO—” refers to the end groupF(CF(CF₃)CF₂O)aCF(CF₃)— of the methyl esterF(CF(CF₃)CF₂O)aCF(CF₃)C(O)OCH3, wherein “a” averages 2 to 15. In someembodiments, a averages between 3 and 10 or a averages between 5 and 8.Such species generally exist as a distribution or mixture of oligomerswith a range of values for a, so that the average value of a may benon-integer. In one embodiment a averages 6.2. This methyl ester has anaverage molecular weight of 1,211 g/mol, and can be prepared accordingto the method reported in U.S. Pat. No. 3,250,808 (Moore et al.), withpurification by fractional distillation. The recitation of numericalranges by endpoints includes all numbers subsumed within the range (e.g.the range 1 to 10 includes 1, 1.5, 3.33, and 10).

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention.

EXAMPLES

All parts, percentages, ratios, etc. in the examples are by weight,unless noted otherwise. Solvents and other reagents used were obtainedfrom Sigma-Aldrich Chemical Company; Milwaukee, Wis. unless specifieddifferently.

Test Methods

Fingerprint Visibility Test

To test the samples, a background haze was measured using a Haze-GardPlus from BYK-Gardner (Columbia, Md.) then a simulated fingerprint wasapplied to the coating and then the haze was again measured using theHaze-Gard Plus. The simulated fingerprint was applied as follows. Asolution was prepared by mixing 0.35 parts Crisco Shortening (J.M.Smucker Company, Orrville, Ohio) with 0.35 parts C₅₇H₁₀₄O₆ (obtainedfrom Sigma Chemical Co., St. Louis, Mo. under the trade designation“Triolein” and 8.0 parts isopropyl alcohol. The solution was coated on127 micron (5 mil) primed PET film using a #10 wire wound rod which wasrapidly pulled across the film. The sample was allowed to dry for 30min. A #5 stopper (from VWR Scientific) having a bottom outer diameterof about 2.3 cm was attached to a plunger (2.5 pound plunger from SummerOptical, Fort Washington, Pa.). The plunger with stopper was pressedonto the coated PET (inking the stopper). Next the plunger was pressedonto the sample to be tested. The haze of the applied simulatedfingerprint was measured immediately and again after 20 minutes. Thefingerprint ratio (FPR) is the ratio of the haze measured after 20minutes to the initial haze. The background haze, the initial haze afterapplying the simulated fingerprint, and the fingerprint ratio may beprovided in the Examples.

Cellulose Haze Test

After the cured coating was prepared it was allowed to equilibrate atambient conditions for 48 hours. Then 0.35 grams of alpha-cellulose(C-8002) from Sigma Chemical Company (St. Louis, Mo.) was applied to thetop of the coating in a 7 cm dia. area. The coated film was tilted backand forth several times to allow the cellulose to evenly coat the 7 cm.dia. test area. The excess cellulose was then shaken off and the haze ofthe coating plus cellulose was measured using a hazemeter according toASTM D1003-11e1, Procedure A.

Steel Wool Durability Test and Results

The abrasion resistance of the cured films was tested cross-web to thecoating direction by use of a mechanical device capable of oscillating asteel wool sheet adhered to stylus across the film's surface. The stylusoscillated over a 60 mm wide sweep width at a rate of 210 mm/sec (3.5wipes/sec) wherein a “wipe” is defined as a single travel of 60 mm. Thestylus had a flat, cylindrical base geometry with a diameter of 3.2 cm.The stylus was designed for attachment of weights to increase the forceexerted by the steel wool normal to the film's surface. The #0000 steelwool sheets were “Magic Sand-Sanding Sheets” available from Hut ProductsFulton, Mo. The #0000 has a specified grit equivalency of 600-1200 gritsandpaper. The 3.2 cm steel wool discs were die cut from the sandingsheets and adhered to the 3.2 cm stylus base with 3M Brand ScotchPermanent Adhesive Transfer tape. A single sample was tested for eachexample, with a 500 g weight and 50 back and forth wipes. The sample wasthen visually inspected for scratches and rated on a 1-5 scale with 5indicating the best durability.

Materials

Nalco 2327—an aqueous dispersion of 20 nm silica nanoparticles (41%solids in water, stabilized with ammonia) obtained from Nalco Chem. Co.Naperville, Ill.

PROSTAB 5198—4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (commonlyreferred to as 4-hydroxy-TEMPO) obtained from CIBA Specialty Chemicals,Tarrytown, N.Y.

Sartomer SR444—pentaerythritol triacrylate (PET3/4) obtained fromSartomer Company, Exton, Pa.

PET film: 127 micron (5 mil) primed PET film prepared according toExample 29 of U.S. Pat. No. 6,893,731.

BHT—2,6-di-t-butyl-4-methylphenol obtained from Sigma Aldrich,Milwaukee, Wis.

Dodecanol, Dibutyltin dilaurate (DBTDL), Glycidol, Phenothiazine, andhydroxyethyl acrylate, Octadecyl acrylate and Octadecyl methacrylatewere obtained from Sigma Aldrich, Milwaukee, Wis.

Catalyst AMC-2 was obtained from Ampac Fine Chemocals, Rancho Cordova,Calif.

2-carboxyethyl acrylic acid (B-CEA) was obtained from Polysciences,Inc., Warrington, Pa.

Brij O2—primary component C₁₈H₃₅(OCH₂CH₂)₂OH (oleyl alcohol with 2ethyleneoxy groups), (calculated HLB 5.4), Brij O5—primary componentC₁₈H₃₅(OCH₂CH₂)₅OH (oleyl alcohol with 5 ethyleneoxy groups) (calculatedHLB 9.3), Brij O10—primary component C₁₈f₁₃₅(OCH₂CH₂)₁₀OH (oleyl alcoholwith 10 ethyleneoxy groups) (calculated HLB 12.9), and Brij S20—primarycomponent C₁₈H₃₇(OCH₂CH₂)₂₀OH (oleyl alcohol with 20 ethyleneoxy groups)(calculated HLB 15.9) were obtained from Croda Inc., Edison, N.J.

VAZO 67, 2,2-azobis(2-methylbutyronitrile) was obtained from DuPont,Wilmington, Del.

Ethyl acetate was obtained from J. T. Baker, Austin, Tex.

EsacureOne—2-hydroxy-1-{11-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-indan-5-yl}-2-methyl-propan-1-onefrom Lamberti SPA, Gallarate, Italy.

PROSTAB 5198—4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (commonlyreferred to as 4-hydroxy-TEMPO) was obtained from CIBA SpecialtyChemicals, Tarrytown, N.Y.

Isocyanatoethyl acrylate (IEA) and isocyanatoethyl methacrylate (IEM)were obtained from CBC America Corp, Commack, N.Y.

Isofol 18T alcohol, a mixture of 2-hexyldecanol, 2-octyldecanol,2-hexyldodecanol, and 2-octyldodecanol (Guerbet alcohol) was obtainedfrom SASOL, Lake Charles, La.

Beta-carboxyethylacrylate (B-CEA) having a titration measured acidequivalent weight of 204.5 was obtained from Polysciences, Inc.,Warrington, Pa.

Components Comprising Low Surface Energy Silicone Group

MCR-C12—Monocarbinol terminated poly(dimethylsiloxane) of 1000 MW fromGelest, Morrisville, Pa.

MCR-C18—Monocarbinol terminated poly(dimethylsiloxane) of 5000 MW fromGelest, Morrisville, Pa.

Preparation of MCR-C12-IEA

Into a 250 ml round-bottom flask was poured 29.99 g (˜0.02999 mols) ofMCR-C12. 393 microliters (1000 ppm) of 10% DBTDL in MEK was added as acatalyst, followed by 3.81 g (0.0269 mols) of isocyanatoethyl acrylate.This ratio of reactants was determined in a small-scale trial in whichthe amount of isocyanate was slowly increased from 0.9 mol fractionuntil a very small isocyanate peak remained via FTIR. Upon addition ofboth reactants the solution became cloudy. The reaction was stirredmagnetically under dry air at 55° C. for 3 hours, at which time ananalysis via FTIR showed no isocyanate was present. The solution wasbrought to 50% solids in ethyl acetate and bottled.

Preparation of MCR-C18-IEA

Into a 250 ml round-bottom flask was poured 30.00 g (˜0.006 mols) ofMCR-C18. 364 microliters (1000 ppm) of 10% DBTDL in MEK was added as acatalyst, followed by 0.98 g (0.0069 mols) of isocyanatoethyl acrylate.This ratio of reactants was determined in a small-scale trial in whichthe amount of isocyanate was slowly increased from 0.9 mol fractionuntil a very small isocyanate peak remained via FTIR. Upon addition ofboth reactants the solution was clear and colorless. The reaction wasstirred magnetically under dry air at 55° C. for 1.5 hours, at whichtime an analysis via FTIR showed no isocyanate was present. Uponcompletion of the reaction the solution had turned white and opaque. Thesolution was brought to 50% solids in ethyl acetate and bottled.

C-3b Methacryloyl terminated poly(dimethylsiloxane) of approximately10,000 MW was prepared by the method outlined for preparation of Monomer“C-3b” in U.S. Pat. No. 4,728,571.

KF-2001—Thiol terminated poly(dimethylsiloxane) of 1900 MW fromShin-Etsu Silicones of America, Akron, Ohio

Components Comprising Low Surface Energy Perfluoroalkyl Group

MeFBSEA (m)—C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂, can be prepared by thegeneral procedure found in U.S. Pat. No. 2,803,613.

Preparation (MeFBSEA)₄SCH₂CH₂OH Oligomer ((FC)4-oligomer)

4 mol parts of MeFB SEA and 1 mol part of thioethanol at 75% solids inethyl acetate were purged with nitrogen for about 5 min, followed by acharge of about 0.5% by weight of VAZO 67, followed by heating at 65°C., for about 15 h.

Preparation of (FC)4-oligomer—IEA

A 250 ml round-bottom flask was charged with 100.02 g (0.0436 mols) of(FC)4-oligomer (estimated molecular weight of 1723 at 100% solids) at75% solids in ethyl acetate,1.22 ml (1000 ppm) of 10% DBTDL in MEK,followed by 5.54 g (0.03926 mols) of isocyanatoethyl acrylate. Thereaction was stirred magnetically under dry air at 55° C. for two hours.At this point the isocyanate was observed by FTIR to have been consumed,so an additional 0.30 g (5%) of IEA was added. After two hours at thesame reaction conditions the isocyanate was again consumed and twoadditional charges were made—0.15 g (2.5%) and 0.30 g (5%)—separated bytwo hours. About 1.5 hours after the last addition the isocyanate peakwas still barely visible but diminished from the FTIR taken immediatelyafter the last IEA addition and the reaction was pronounced complete.The product was brought to 50% solids with ethyl acetate and bottled.

Component Comprising Low Surface Energy Perfluoroether Group

Preparation of HFPO Amidol Acrylate

HFPO—C(O)N(H)CH₂CH₂OH (HFPO amidol) with molecular weight 1420 was madeby a procedure similar to that described in U.S. Pat. No. 7,098,429(Audenaert, et al.), the disclosure of which is incorporated herein byreference, for the synthesis of HFPO-oligomer alcohols with theexception that the HFPO methyl ester F(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)OCH₃with a=6.2 was replaced with F(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)OCH₃ wherea=7.3. The HFPO methyl ester was prepared according to the methodreported in U.S. Pat. No. 3,250,808 (Moore, et al.), the disclosure ofwhich is incorporated herein by reference, with purification byfractional distillation.

HFPO Acrylate (also referred to as HFPO-A was made from the HFPO amidolusing the procedure described in Preparative Example 2 of U.S. Pat. No.6,995,222 (Buckanin, et al.).

Components Comprising Hydroxyl Group(s)

Hydroxybutyl acrylate was obtained from TCI America, Portland, Oreg.

Hydroxyethyl acrylate was obtained from Sigma-Aldrich, Milwaukee, Wis.

Preparation of B-CEA-1.42 Glycidol (also referred to as B-CEA-1.42 GLY)

Into a 1-liter, three-neck round bottom flask was poured 198.14 g (0.967mol, 204.8 acid equivalent weight) beta-carboxyethylacrylate. Next, 1.49g (0.5% by weight) of AMC-2 catalyst was added, and the reaction was setstirring at 95° C. via mechanical, overhead stirring in a silicone oilbath. The reaction was kept under dry air throughout. Into a pressureequalized dropping funnel, 101.83 g (1.374 mols, 74.08 MW, 1.42equivalents compared to the B-CEA) of glycidol was charged. The glycidolwas added via the dropping funnel at a steady rate over 55 minutes. Thereaction was stirred at 95° C. for three hours after the end of theglycidol addition, at which point a sample was taken for analysis.Analysis via ¹H NMR in CDCl₃ showed negligible amounts of remainingreactants and 286.31 g of solution were bottled.

Beta-carboxyethylacrylate is available as a distribution of productsthat includes acrylic acid, beta-carboxyethylacrylate, and higheroligomers. The beta-carboxyethylacrylate from Polysiciences used herehas a titration measured acid equivalent weight of 204.5. Its reactionwith glycidol is expected to largely provide the distribution ofmaterials pictured below.

Components Comprising Alkyl Group

Lauryl acrylate was obtained as SR335 from Sartomer, Exton, Pa.

Preparation of Hexanol-IEA

Into a 1-liter round bottom flask was added 2.1 ml of 10% DBTDL in MEKsolution. To that, 0.1779 g (0.5% by weight of reactants) of BHT wasadded. 149.99 g (1.468 mols) of hexanol (calculated HLB=4.9) was added,followed by 357.19 g ethyl acetate. Finally 207.16 g (1.468 mols) ofisocyanatoethyl acrylate was added, bringing the solution to 50% solids.The reaction was stirred magnetically at 65° C. in a silicone oil bathand kept under dry air. The reaction was clear and colorless throughout.After 15 minutes, the reaction temperature was turned down to 50° C. toprevent boiling of ethyl acetate (some solvent lost). After 45 minutes,a sample was taken and analyzed via FTIR. No isocyanate peak was presentso the reaction was stopped. 157.53 g of ethyl acetate were added tobring the solution to 50% solids and 702.38 g of solution was bottled.The structure below illustrates the type of product obtained fromreactions of alcohols with IEA.

Preparation of Dodecanol-IEA

Into a 1-liter round bottom flask was added 2.05 mL of 10% DBTDL in MEKsolution. To that, 0.1777 g (0.5% by weight of reactants) of BHT wasadded. 199.99 g (1.0733 mols) of dodecanol (calculated HLB=2.1) wasadded, followed by 351.40 g ethyl acetate. Finally 151.48 g (1.0733mols) of isocyanatoethyl acrylate was added, bringing the solution to50% solids. The reaction was stirred magnetically at 60° C. in asilicone oil bath and kept under dry air. The reaction was clear andcolorless throughout. After 15 minutes, the reaction temperature wasturned down to 50° C. to prevent boiling of ethyl acetate. After 1 hour,a sample was taken and analyzed via FTIR. The FTIR analysis showed noisocyanate peak was present and the reaction was stopped. 700.03 g wasbottled.

Preparation of Guerbet C18-IEA

The acrylate of Isofol 18T was prepared as described in U.S. Pat. No.8,137,807 (Clapper, et al.) for Method 1, Monomer GM4.

Into a 1-liter round bottom flask was added 1.80 mL of 10% DBTDL in MEKsolution. To that, 0.1490 g (0.5% by weight of reactants) of BHT wasadded. 199.98 g (0.7586 mols) of Isofol 18T was added, followed by307.06 g ethyl acetate. Finally 107.05 g (0.7586 mols) ofisocyanatoethyl acrylate was added, bringing the solution to 50% solids.The reaction was stirred magnetically at 50° C. in a silicone oil bathand kept under dry air. The reaction was clear and colorless throughout.After 1.25 hours, a sample was taken and analyzed via FTIR. The FTIRanalysis showed no isocyanate peak was present and the reaction wasstopped. 605.56 g was bottled.

Components Comprising Hydrophobic Group and Alkylene Oxide Units

Synthesis of Polymerizable Surfactant Brij O2 Acrylate

To a 11 round bottom flask equipped with magnetic stirbar and heat-tapewrapped Dean-Stark trap with condenser was added 200 g (0.561 mol) BrijO2, 41.22 g (0.572 mol) acrylic acid, 0.05 g BHT (˜500 ppm based onsolids), 0.05 g phenothiazine, and 300 g heptane. The reaction washeated in an oil bath. When the internal temperature was about 80° C.,2.96 g (0.0308 mol) methanesulfonic acid was added to the reaction. Theoil bath was raised to 120° C., and the heating tape was turned on.After 4 h of refluxing, 10.0 ml of water was collected, the reaction wascooled to 80° C., and 4.69 g (0.0314 mol) triethanolamine was added withstirring to the reaction. After 5 min, 120 g of deionized water wasadded to the reaction, which was stirred for 1 min, transferred to aseparatory funnel, shaken and allowed to settle overnight. Three layersresulted: a clear aqueous layer (84.2 g), and an interphase with a browngooey mixture (48.7 g), and a top light brown layer. The top layer wasisolated and heated in a flask with 120 g of 2% aqueous sodium carbonateto 80° C. T mixture was allowed to settle in the separatory funnel withheating to 75° C. The layers were separated, and the aqueous layer wasre-extracted with 50 g of heptane. The combined heptane layers weredried over anhydrous magnesium sulfate, filtered and concentrated on arotary evaporator to yield 209.7 g (91.1% yield) of a light brown oil,which was characterized by ¹H NMR. The calculated hydrophilic-lipophilicbalance (HLB) of this surfactant is 5.6, assuming two ethylene oxiderepeat units.

Preparation of Brij O5-IEA

Into a 500 mL round bottom flask was poured 50.00 g (0.1021 mols)C₁₈H₃₅O(CH₂CH₂O)₅H and 64.41 g MEK. A line was placed on the flask toindicate the level of the solution, and about 40 g more MEK was added.Removal of excess MEK was done azeotropically by boiling off MEK at 95°C. until the level of the solution was just below the original linedrawn on the flask. 250 μL 10% DBTDL in MEK solution was added followedby 12 mg BHT and 14.41 g (0.100 mol) isocyanatoethyl acrylate in 2 g ofMEK. The reaction was stirred magnetically in a 60° C. silicone oil bathfor about 3 hours at which point a sample was taken for analysis. FTIRanalysis showed no isocyanate peak and the reaction was stopped. Thesolution was adjusted to 50% solids with the addition of 18.68 g MEK andbottled.

Preparation of Brij O5 Acrylate

A 1.0-liter round bottom flask was charged with 250 g (0.5117 mols) BrijO5, 250 g heptane, 37.66 g (0.5220 mols) acrylic acid, 0.0575 g MEHQ and0.0575 g Prostab 5198 inhibitor. The reaction was heated to 120° C. in asilicone oil bath. The flask was topped by a Dean-Stark (D-S) trapwrapped in heat tape with a condenser atop the D-S trap. When thereaction was warm, 3.42 g (0.03558 mols) of methanesulfonic acid wascharged and reaction was run for 4.5 hours. 9.4 mL had collected in theD-S trap. The reaction temperature was dropped to 90° C. and 5.55 g(0.0372 mols) of triethanolamine was added. The reaction was thenstirred for 5 minutes at which point the reaction was heated to 70° C.and 100 g of distilled water was added. The reaction was poured into aseparatory funnel, resulting in a yellow top layer and whitish bottomlayer. The layers were allowed to separate over 1 hour. 25 g ofsaturated brine was added to help clean out the bottom layer and theseparatory funnel was tilted a few times and left to separate overnight.The organic layer weighed 498.8 g. The top layer was heated in a 90° C.silicone oil bath while stirred. When heated to 70° C., 100 g of 2%Na₂CO₃ solution was added along with 6 g of a 1:5 mixture of 2% Na₂CO₃:organic layer used to determine a best-method for the split. Thesolution was stirred for 3.5 minutes to an internal temperature of 65°C. and then poured into a 1-liter separatory funnel. By a combination ofheating and stirring, a clean lower layer, whitish middle, and yellowtop layer appeared. The next day a good separation had occurred and 20 gsilica gel was added to the organic layer and stirred at 50° C. in asilicone oil bath. Six type C fritted Buchner funnels were used tofilter the material (funnels were used until too plugged to filter). Thefunnels were rinsed with heptane and the material was concentrated on arotary evaporator at 93° C. and 28 in Hg. The yield was 212.24 g. Thecalculated hydrophilic-lipophilic balance (HLB) of this surfactant is9.2.

Preparation of Brij O10-IEA

Into a 250 mL round bottom flask was poured 50.00 g (0.1021 mols)C₁₈H₃₅O(CH₂CH₂O)₁₀H and 59.94 g MEK. A line was placed on the flask toindicate the level of the solution, and about 40 g more MEK was added.Removal of excess MEK was done azeotropically by boiling off MEK at 95°C. until the level of the solution was just below the original linedrawn on the flask. 220 μL 10% DBTDL in MEK solution was added, followedby 10 mg BHT and 14.41 g (0.100 mol) isocyanatoethyl acrylate. Theaddition flask was rinsed with 2 g MEK and the reaction was stirredmagnetically in a 55° C. silicone oil bath for about 3 hours at whichpoint a sample was taken for analysis. FTIR analysis showed noisocyanate peak and the reaction was stopped. The solution was adjustedto 50% solids with the addition of 22.11 g MEK and bottled.

Preparation of Brij O10 Acrylate

A 1.0-liter round bottom flask was charged with 250 g (0.352 mols) BrijO10, 250 g heptane, 15.88 g acrylic acid (0.359 mols), 0.0552 g MEHQ and0.0552 g Prostab 5198 inhibitor. The reaction was heated to 120° C. in asilicone oil bath. The flask was topped by a Dean-Stark trap wrapped inheat tape with a condenser atop the D-S trap. When the reaction waswarm, 3.58 g (0.03725 mols) of methanesulfonic acid was charged andreaction was run for 8 hours. The next day, 8.2 mL had collected in theD-S trap. The reaction was heated to 52° C. and 5.72 g (0.0383 mols) oftriethanolamine was added. The reaction was then stirred for 5 minutesat which point the reaction was heated to 80° C. and 50 g of water wasadded. A separation over several hours resulted in a small bottom layer(˜18 g). The top layer was treated with 50 g of silica gel and thenfiltered through a type C fritted Buchner funnel. 10 different filterswere needed to complete the filtration due to clogging. The next day thematerial was condensed on a rotary evaporator at up to 90° C. and 85 kPa(25 in. Hg) vacuum to provide a light brownish oil with a small amountof particles. The calculated hydrophilic-lipophilic balance (HLB) ofthis surfactant is 12.5.

Preparation of Brij S20-IEA

In a 500 ml round bottom flask, 100.00 g (0.0944 mols) dried, moltenBrij S20 was added to 113.33 g ethyl acetate. The solution was put intoa 60° C. silicone oil bath and stirred magnetically under dry air. Tothe stirring solution was added 0.0567 g BHT and 0.0567 g 10% DBTDL inMEK. 13.33 g (0.0944 mols) of isocyanatoethylacrylate was added to adropping funnel and added to the reaction over 10 minutes. The droppingfunnel was rinsed with 1.5 g ethyl acetate. After reaction overnight,analysis was done via FTIR which showed no isocyanate peak. The reactionwas brought to 50% solids and bottled.

Synthesis of Non-Ionic Surfactant

To a 250 ml round bottom flask equipped with an overhead mechanicalstirrer, temperature probe and Dean-Stark trap with condenser was added50 grams (0.177 moles) 90% oleic acid (technical grade), 0.168 moles(0.95 equivalents) of diethyleneglycol monoethyl ether, 100 gramscyclohexane, and 1.5 grams para-toluene sulfonic acid. The batch washeated to reflux with moderate agitation to azeotrope off water from theesterification and water was collected in a dean-stark trap. After fourhours of reflux, a total of 3 grams of water had been collected and nofurther water was being produced. Liquid chromatography showed a smallamount of residual oleic acid.

The reaction was allowed to cool to room temperature. To the flask amixture of 60 grams water and 6 grams sodium carbonate was added and 4.5grams isopropyl alcohol was added. The contents of the flask were mixedwell and then allowed to phase separate in a separatory funnel. Thelower aqueous layer was removed. Then a mixture of 70 grams saturatedsodium chloride in water was added, the flask shaken, and the contentsallowed to separate. The lower aqueous layer was removed. The residualcyclohexane solvent was removed from the ester product using arotary-evaporator to provide 58 g of a light yellow colored product.Liquid chromatography showed no residual oleic acid. The calculatedhydrophilic-lipophilic balance (HLB) of this surfactant is 4.7.

Polymerizable Surfactant BrijO2 Acrylate

Synthesis previously described.

Preparation of Surface Modified Nanosilica Dispersion

305 grams of Nalco 2327 was added to a 1-liter reaction flask. 486 gramsof 1-methoxy-2-propanol was added to the reactor with stirring. 19.38grams of 3-methacryloxypropyltrimethoxysilane was added slowly to thereactor with stirring. 0.15 grams of a 5% aqueous of PROSTAB 5198 wasadded to the reactor with stirring. The mixture was stirred 18 hours at90° C.

The reaction mixture was heated under vacuum and the1-methoxy-2-propanol/water azeotrope was distilled off with anynecessary addition of 1-methoxy-2-propanol to remove substantially allof the water. The surface modification reaction resulted in a mixturecontaining 40% surface modified silica (20 nm average particle size), byweight, in 1-methoxy-2-propanol.

Preparation of SiO2/SR444

Surface modified nanosilica in Sartomer SR444 was prepared by mixingSartomer SR444 and the 1-methoxy-2-propanol dispersion of surfacemodified nanosilica described in “Surface Modified NanosilicaDispersion” with weight ratios of 30 modified silica to 70 SR 444. The1-methoxy-2-propanol was then evaporated using a rotary-evaporator.

Examples 1-15

The HFPO copolymer for Example 1 was synthesized as follows. In a cleanglass reaction bottle were added 0.125 grams of dodecanethiol, 20.0grams of a 50% solids solution of HFPO amidol-acrylate in EtOAc (Ethylacetate), 10 grams of a 50% solids solution of B-CEA-1.42 Glycidol inEtOAc, 20 grams of a 50% solution of dodecanol-IEA in Ethyl Acetate,0.125 grams of VAZO 67 and 25 grams of EtOAc. The solution was purgedwith nitrogen for two minutes. The bottle was sealed and placed in aconstant temperature water bath with a rotating device. The solution washeated at 65° C. for 16 hours and then cooled to room temperature. Amedium viscous polymer solution was obtained.

Half of this 75.25 grams of solution (37.625 grams, containing 12.625grams solids) This solution was charged into a 50 mL amber jar equippedwith a magnetic stirbar along with 75 microliters of 10% DBTDL in MEK,and 0.25 grams of IEA and placed in an oil bath at 55° C. for 1 hr 15min. At that time, the reaction was monitored for completeness bydisappearance of an isocyanate peak in the FTIR spectrum of the sample.The reaction was adjusted to 30% solids with 5.29 grams ethyl acetate.

Using the procedure described for Example 1, HFPO copolymers forExamples 2-15 were made by preparing a solution of the materials in thetable below except for IEA with the addition of 25 parts EtOAc, 0.125parts VAZO 67, 0.125 parts Dodecane-thiol. The resulting solution wasreacted with DBTDL and IEA as described in Example 1 with the weightparts IEA indicated in the table below. After the reaction was completeit was adjusted to 30% solids with 10.58 weight parts ethyl acetate. Allparts are by weight of solution and all materials at 50% solids exceptVAZO 67, dodecane-thiol and IEA.

Ex- HFPO B-CEA- Dodec- am- Acry- 1.42 Additional Additional anol- plelate Glycidol Acrylate Acrylate IEA IEA 1 20 10 — — 20 0.5 2 20 10 BrijO10-IEA 5 15 0.5 3 20 10 Brij O2 5 15 0.5 acrylate 4 15 10 Brij S20-IEA10 15 0.5 5 15 10 Brij O5-IEA 10 15 0.5 6 15 10 Brij O10-IEA 10 15 0.5 715 10 Brij O2 10 15 0.5 acrylate 8 20 0 Hydroxyethyl 10 20 0.5 acrylate9 20 0 Hydroxybutyl 10 20 0.5 acrylate 10 20 0 Hydroxyethyl 15 15 0.5acrylate 11 20 0 Hydroxybutyl 15 15 0.5 acrylate 12 20 10 Brij S20-IEA 515 0.5 13 20 10 Brij O5 5 15 0.5 acrylate 14 20 10 Brij O5-IEA 5 15 0.5308 15 20 10 Brij O10 5 15 0.5 acrylate

For each of Examples 1-15, the HFPO copolymer additives were formulatedinto an anti-fingerprinting coating formulation according to thefollowing table:

Amount Solids (parts by Material weight) SiO₂/SR 444 77.43 Esacure One2.15 Non-Ionic Surfactant 12.4 Polymerizable Surfactant 7.9 Brij O2Acrylate HFPO Copolymer 0.036 Additive

Coating solutions were made by dissolving the materials listed in theabove table in ethanol at 65% solids. These solutions were coated on aprimed 127 micron (5 mil) PET film. The coatings were coated at a drythickness of about 15 microns using a #18 wire wound rod. The coatingswere dried in an air circulating oven at 105° C. for two minutes. Thecoatings were then were UV cured using a nitrogen purged Fusion LightHammer® 6 with a 500 watt Fusion H bulb (Fusion UV Systems, Inc.,Gaithersburg, Md.) and placed on the conveyer at 12.2 m/min (40 ft/min).

The Fingerprint Test and the Cellulose Haze Test were performed on thesamples. The cellulose haze and the ratio of the fingerprint after 20minutes to the initial fingerprint (FPR) are reported in the tablebelow.

Example Cellulose Haze FPR 1 1 0.40 2 14 0.38 3 13 0.29 4 5 0.31 5 90.37 6 10 0.40 7 1 0.41 8 4 0.44 9 4 0.43 10 4 0.37 11 1 0.42 12 6 0.4613 10 0.58 14 7 0.68 15 13 0.76

Examples 16-20 and Comparative Examples C1-C2

The formulation for the copolymer batch used for Examples 16-22 wereprepared according to the table below using a procedure similar to thatfor the preparation of the HFPO copolymer of Example 1. All materialswere at 50% solids in ethyl acetate except for the VAZO 67 anddodecane-thiol.

Material Amount (grams) HFPO Acrylate 65.86 Solution HydroxybutylAcrylate 74.14 Solution Lauryl Acrylate (SR 60 335) Solution EtOAc 100VAZO 67 0.5 Dodecane-thiol 0.5

The HFPO copolymers for Examples 16-22 were prepared by reacting theamount of IEM shown in the table below with one-eighth of the batchdescribed above. After the reaction was complete, EtOAc was added in theamount shown in the table below to bring the solution to 30% solids.

Example C1 16 17 18 19 20 C2 IEM (g) 0 0.25 0.5 1.25 2.49 3.74 4.99EtOAc (added to bring 4.46 5.29 6.13 8.64 12.77 16.93 21.08 to 30%solids) (g) Mole fraction of OH 0 0.05 0.10 0.25 0.50 0.75 1.00 groupsreacted with IEM Calculated OH EW 393 422 454 576 941 2037 infinite

The amount of IEM required to produce a specified mole fraction of OHgroups reacted with IEM was determined as follows. The copolymer batchcontained 37.07 g hydroxybutyl acrylate or 0.2571 mol hydroxyl groups(37.07 g/144.17 g/mol). One-eighth of the batch contained 37.63 g ofsolution (301 g/8). Each 37.63 g of solution contained 0.03214(0.2571/8) moles of hydroxyl groups. For Example 16, the mole fractionof OH groups reacted with IEM was 0.05. The number of moles of IEMrequired to achieve this was determined as 0.05 times 0.03214 moles,which gives 1.607×10⁻³ moles of IEM. Since the molecular weight of IEMis 155.15, the required mass of IEM was 1.607×10⁻³ moles times 155.15g/mole or 0.25 grams. The OH Equivalent Weight (EW) was calculated asmass of solids in the solution divided by the number of moles of OH thatwas not reacted with IEM. For Example 16, the number of moles of OH thatwas not reacted with IEM was 0.03053 (0.0321 times 0.95) and the totalmass of solids was 12.88 grams, so the OH EW was 422 (12.88/0.03053).The other examples were determined similarly. For Example C2 where allhydroxyl groups were reacted with IEM, the amount of IEM required was4.99 g (0.03214 moles times 155.15 g/mol).

For the hydroxybutyl acrylate units unreacted with IEM the formula forthose units is:

For the hydroxybutyl acrylate units reacted with IEM the formula forthose units is:

The HFPO copolymers described above were used to make coating solutionsin the same manner and proportions as described in Examples 1-15. Thecoated solutions were then used to make coated films as described inExamples 1-15. The Fingerprint Test and the Cellulose Haze Test wereperformed on the samples. The initial fingerprint (Initial FP), theratio of the fingerprint after 20 minutes to the initial fingerprint(FPR), the cellulose haze and the background haze are reported in thetable below.

Initial Cellulose Background Example FP FPR Haze Haze C1 9.8 0.84 2.50.3 16 9.4 0.53 1 0.3 17 10.1 0.47 3 0.3 18 11.2 0.42 2.1 0.3 19 9.90.39 46 0.3 20 9.9 0.35 45 0.3 C2 11.1 0.38 51 0.3

Examples 21-32

Using the procedure described in Example 1, HFPO copolymers for each ofExamples 21-32 were made by preparing a solution of the materials in thetable below except for IEA with the addition of 25 parts EtOAc, 0.125parts VAZO 67, 0.125 parts Dodecane-thiol The resulting solution wasreacted with DBTDL and IEA as described in Example 1 with the weightparts IEA indicated in the table below. After the reaction was completeit was adjusted to 30% solids with 10.58 weight parts ethyl acetate. Allparts are by weight of solution and all materials at 50% solids exceptVAZO 67, dodecane-thiol and IEA.

Example 21 22 23 24 25 26 27 28 29 30 31 32 HFPO Acrylate 20 20 20 20 2020 20 20 20 20 20 20 B-CEA Glycidol 10 10 10 10 10 1.42 Hydroxybutyl 1515 15 15 15 15 15 acrylate Dodecanol-IEA 20 15 Hexanol-IEA 15 20 GuerbetC18 15 20 alcohol-IEA Lauryl acrylate 15 20 (SR 335) Guerbet C18 15acrylate Octadecyl (C18) 15 acrylate (ODA) Octadecyl (C18) 15 20methacrylate (ODMA) IEA 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

The HFPO copolymers in the above table were used to make coatingsolutions in the same manner and proportions as described in Examples1-15. The coated solutions were then used to make coated films asdescribed in Examples 1-15. The Fingerprint Test and the Cellulose Hazetest were performed on the samples. The background haze, the cellulosehaze and the ratio of the fingerprint after 20 minutes to the initialfingerprint are reported in the table below. For Examples 21 and 22,samples were made from two separate batches (labeled Examples 21a and21b for the two samples for Example 21 and labeled 22a and 22b for thetwo samples of Example 22).

Cellulose Example Haze Haze FPR 21a 0.24 1.0 0.25 21b 0.24 1.6 0.28 22a0.21 7.7 0.35 22b 0.21 0.7 0.33 23 0.2 1.5 0.23 24 0.23 1.1 0.32 25 0.265.9 0.35 26 0.22 1.8 0.30 27 0.21 4.3 0.31 28 0.26 2.3 0.32 29 0.2 1.10.33 30 0.23 14 0.27 31 0.22 0.6 0.30 32 0.22 3.6 0.41

Examples 33-38

Using the procedure described in Example 1, HFPO copolymers for each ofExamples 33-38 were made by preparing a solution of the materials in thetable below except for IEM. The resulting solution was reacted withDBTDL and IEM as described in Example 1 except that IEM was used insteadof IEA with the weight parts IEM indicated in the table below. All partsare by weight of solution and all materials at 50% solids except VAZO67, dodecane-thiol and IEM. After the reaction was complete it wasadjusted to 30% solids with 10.58 weight parts ethyl acetate.

Example 33 34 35 36 37 38 HFPO Acrylate 10 20 15 10 15 20 Hydroxybutyl 55 25 15 15 15 acrylate (HBA) Lauryl acrylate 35 25 10 25 20 15 (SR 335)Butyl acrylate 25 20 15 EtOAc 25 25 25 25 25 25 VAZO 67 0.125 0.1250.125 0.125 0.125 0.125 Dodecane-thiol 0.125 0.125 0.125 0.125 0.1250.125 IEM 0.5 0.5 0.5 0.5 0.5 0.5

The hydroxyl equivalent weight (OH EW) of the additives for Examples 33and 34 were calculated in the following fashion. For each of Examples 33and 34, hydroxybutyl acrylate made up 10% by weight of the monomers.Batches of the polymers of Examples 33 and 34 containing 25 g ofmonomers, each contained 2.5 g of hydroxybutyl acrylate (10% of 25 g is2.5 g). Therefore each batch contained 2.5 g/144.17 g/mol (MW forhydroxybutyl acrylate)=0.01734 mol OH groups. Reacting each batch with0.5 g (0.003223 mol) of IEM (MW 155.15) resulted in some of the OHgroups being functionalized to provide curable functionality, leaving0.01734-0.00322=0.01412 moles hydroxyl groups. The total weight of allmaterial in the batches for Examples 33 and 34 that each contained 25 gof monomers was 25.75 g (25 g monomers, 0.125 g VAZO 67, 0.125 gdodecane thiol, and 0.5 g IEM). Thus the OH EW for the additives ofExample 33 and 34 was 25.75 g/0.01412 mol OH=1823.7 g/mol.

The hydroxyl equivalent weight (OH EW) of additive 35 was calculated inthe following fashion. For Examples 35, hydroxybutyl acrylate made up50% by weight of the monomers. A batch of the polymers of Example 35containing 25 g of monomers, contained 12.5 g of hydroxybutyl acrylate(50% of 25 g is 12.5 g). Therefore the batch contained 12.5 g/144.17g/mol=0.0867 mol OH groups. Reacting with 0.5 g (0.003223 mol) of IEM(MW 155.15) resulted in some of the OH groups being functionalized toprovide curable functionality. The total weight of all material in thebatch containing 25 g of monomers was 25.75 g. Thus the OH EW for theadditive of Example 35 was 25.75 g/0.083477 mol OH=308.5 g/mol.

Example 35 could alternatively be prepared by replacing hydroxybutylacrylate with hydroxyethyl acrylate. In this case the OH EW could becalculated in the following fashion. For a batch of polymer withmonomers weighing 25 g, there would be 12.5 g hydroxyethyl acrylate (50%of 25 is 12.5 g). This gives 12.5 g/116.12 g/mol (MW for hydroxyethylacrylate)=0.1076 mol OH groups. Reacting with 0.5 g (0.003223 mol) ofIEM (MW 155.15) results in some of the OH groups being functionalized toprovide curable functionality. The total weight of all material in abatch containing 25 g of monomers is 25.75 g. Thus the OH EW for thisadditive is 25.75 g/0.104377 mol OH=246.7 g/mol.

The HFPO copolymers in the above table were used to make coatingsolutions in the same manner and proportions as described in Examples1-15. The coated solutions were then used to make coated films asdescribed in Examples 1-15. The Fingerprint Test and the Cellulose HazeTest were performed on the samples. Initial fingerprint (Initial FP),the ratio of the fingerprint after 20 minutes to the initial fingerprint(FPR), the cellulose haze and the background haze are reported in thetable below.

Initial Cell. Example FP FPR Haze Haze 33 11.2 0.28 17 0.7 34 12.6 0.411.1 1 35 12.5 0.42 11.1 0.2 36 12.4 0.57 20 0.3 37 10.9 0.65 1.6 0.4 3810.1 0.41 14.2 0.2

Examples 39-41 and Comparative Example C3

For Comparative Example C3, additive 5 of U.S. patent application Ser.No. 13/307,137 was used as the HFPO additive. For Example 39, the HFPOcopolymer of Example 25 was used. For each of Examples 40 and 41, anHFPO copolymer was made by preparing a solution of the materials in thetable below except for IEM as described in Example 1. The resultingsolution was reacted with DBTDL and IEM as described in Example 1 exceptthat IEM was used instead of IEA with the weight parts IEM indicated inthe table below. After the reaction was complete it was adjusted to 30%solids with 10.58 weight parts ethyl acetate. All parts are by weight ofsolution and all materials at 50% solids except VAZO 67, dodecane-thioland IEM.

Example 40 41 HFPO Acrylate-50% 25 23.54 solids in ethyl acetateHydroxybutyl acrylate- 15 18.54 50% solids in ethyl acetate Laurylacrylate-50% 10 7.93 solids in ethyl acetate EtOAc 25 25 VAZO 67 0.1250.125 Dodecane-thiol 0.125 0.125 Isocyanatoethyl 0.5 0.5 methacrylate(IEM)

After formulation of the acrylate copolymers, coating formulations wereprepared as in Example 1 and a number of formulations were machinecoated. Sample formulations were slot-die coated using the followingmethod: The liquid coating composition was coated onto 125 micron gauge(5 mil) polyester film using a slot-fed die coater at a wet coatingthickness of approximately 23 microns at a web speed of approximatelynine meters per minute (30 feet/minute) to provide a dry thickness of 15microns. The coated web was dried by passing through a gap dryer (asdescribed in U.S. Pat. Nos. 5,581,905; 5,694,701 and 6,134,808) set atapproximately 60° C. (residence time in the gap dryer was approximately20 seconds). Then the web was further dried by passing through aconventional drying oven set at 100° C. (oven residence time wasapproximately 40 seconds). The coating was cured inline on the polyesterweb using a Fusion Processor with a 600-watt H bulb (both available fromFusion UV Systems of Gainsburg, Md.). The cellulose haze test wasperformed after equilibrating at ambient conditions for 24, 48 and 168hours after coating. The results are reported in the table below.

Cellulose Cellulose Cellulose Haze Haze Haze Example Haze 24 Hours 48Hours 168 hours 39 0.59 0.9 1.1 3.5 40 0.59 7.3 1.7 2.1 41 0.62 17 27 29C3 0.61 56 78 74

C3 is the HFPO urethane acrylate of Additive 5 of U.S. PatentApplication Publication US2012/0154811.

Examples 42-49

Using the procedure described in Example 1, HFPO copolymers for each ofExamples 42-49 were made by preparing a solution of the materials in thetable below except for IEM. The resulting solution was reacted withDBTDL and IEM as described in Example 1 except that IEM was used insteadof IEA with the weight parts IEM indicated in the table below. After thereaction was complete it was adjusted to 30% solids with 10.58 weightparts ethyl acetate. All parts are by weight of solution and allmaterials at 50% solids except VAZO 67, dodecane-thiol and IEM.

Example 42 43 44 45 46 47 48 49 MeFBSEA 20 15 (FC)4-oligomer-IEA 20 15MCR-C12-IEA (1000 20 15 MW Silicone) MCR-C18-IEA (5000 20 15 MWSilicone) Hydroxybutyl 15 15 15 15 15 15 15 15 acrylate (HBA) Laurylacrylate 15 20 15 20 15 20 15 20 (SR 335) Ethyl acetate 25 25 25 25 2525 25 25 VAZO 67 0.125 0.125 0.125 0.125 0.125 0.125 0.125 0.125Dodecane-thiol 0.125 0.125 0.125 0.125 0.125 0.125 0.125 0.125 IEM 0.50.5 0.5 0.5 0.5 0.5 0.5 0.5

The HFPO copolymers in the above table were used to make coatingsolutions in the same manner and proportions as described in Examples1-15. The coated solutions were then used to make coated films asdescribed in Examples 1-15. The Fingerprint Test and the Cellulose HazeTest were performed on the samples. Initial fingerprint (Initial FP),the ratio of the fingerprint after 20 minutes to the initial fingerprint(FPR), the background haze and the cellulose haze are reported in thetable below.

Initial Cellulose Example FP FPR Haze Haze 42 5.32 0.28 0.27 38.00 434.86 0.33 0.2 22.00 44 4.52 0.34 0.22 36.00 45 3.99 0.30 0.25 30.00 466.87 0.41 0.23 3.90 47 6.36 0.44 0.2 2.80 48 6.38 0.53 0.17 7.50 49 5.700.51 0.2 10.70

Examples 50-62

Using the procedure described in Example 1, HFPO copolymers for each ofExamples 50-62 were made by preparing a solution of the materials in thetables below except for IEM. The resulting solution was reacted withDBTDL and IEM as described in Example 1 except that IEM was used insteadof IEA with the weight parts IEM indicated in the tables below. Afterthe reaction was complete it was adjusted to 30% solids with 10.58weight parts ethyl acetate. All parts are by weight of solution and allmaterials at 50% solids except VAZO 67, dodecane-thiol and IEM.

Example 50 51 52 53 54 55 56 HFPO acrylate 10 MeFBSEA 10(FC)4-oligomer-IEA MCR-C18-IEA (5000 10 7.5 10 10 MW Silicone) C-3b 2010 KF-2001 20 Hydroxybutyl 20 22.5 15 15 15 20 15 acrylate Laurylacrylate 20 20 15 15 15 20 15 (SR 335) Ethyl acetate 25 25 25 25 25 2525 VAZO 67 0.125 0.125 0.125 0.125 0.125 0.125 0.125 Dodecane-thiol0.125 0.125 0.125 0.125 0.125 0.125 0.125 IEM 0.5 0.5 0.5 0.5 0.5 0.50.5 Example 57 58 59 60 61 62 HFPO acrylate 10 10 MeFBSEA 10 10(FC)4-oligomer-IEA 10 10 10 MCR-C18-IEA (5000 10 MW Silicone) C-3bKF-2001 10 20 Hydroxybutyl 20 15 15 15 15 15 acrylate Lauryl acrylate 2015 15 15 15 15 (SR 335) Ethyl acetate 25 25 25 25 25 25 VAZO 67 0.1250.125 0.125 0.125 0.125 0.125 Dodecane-thiol 0.125 none 0.125 0.1250.125 0.125 IEM 0.5 0.5 0.5 0.5 0.5 0.5

The HFPO copolymers in the above table were used to make coatingsolutions in the same manner and proportions as described in Examples1-15. The coated solutions were then used to make coated films asdescribed in Examples 1-15. The Fingerprint Test and the Cellulose HazeTest were performed on the samples. Initial fingerprint (Initial FP),the ratio of the fingerprint after 20 minutes to the initial fingerprint(FPR), the background haze, the cellulose haze, the Steel WoolDurability Test results and are reported in the table below.

Steel Wool Initial Durability Example FP FPR Haze Cellulose haze 1-5, 5best 50 6.97 0.32 0.17 29 3 51 9.02 0.38 0.23 29 4 52 7.24 0.38 0.22 1.13 53 8.57 0.39 0.20 25 4 54 7.12 0.36 0.17 20 4 55 8.73 0.32 0.17 8.5 456 8.44 0.38 0.17 4.8 4 57 9.45 0.40 0.18 1 3 58 9.02 0.40 0.17 .6 4 598.68 0.37 0.18 3.5 3 60 9.08 0.43 0.22 1.9 2 61 8.82 0.42 0.23 3.5 2 629.59 0.42 0.19 13 2

What is claimed is:
 1. A copolymer additive comprising units representedby the general formula:-[M^(L)]_(l)-[M^(OH)]_(q)-[M^(A)]_(p)-[M^(R4)]_(o)- wherein l, q, p, ando are each at least 1; and [M^(L)] represent units derived from one ormore ethylenically unsaturated monomers comprising a group selected fromorganopolysiloxane, perfluoroalkyl, and perfluoropolyether; [M^(OH)]represent units derived from one or more ethylenically unsaturatedmonomers and at least one hydroxyl group; [M^(A)] represent unitsderived from [M^(OH)] wherein a portion of the hydroxyl groups areconverted to free-radically polymerizable groups; and [M^(R4)] representunits derived from one or more ethylenically unsaturated monomerscomprising an alkyl group.
 2. The copolymer additive of claim 1 whereinthe copolymer additive further comprises [M^(AO)] that represents unitsderived from one or more ethylenically unsaturated monomers having thegroup R—(O—Ra)_(j)— wherein R is an alkyl group having greater than 6carbon atoms, Ra is independently an alkylene group C_(x)H_(2x) wherex=2 to 4, and j ranges from 1 to
 50. 3. The copolymer additive of claim1 wherein the ethylenically unsaturated monomers of [M^(L)] and[M^(OH)], [M^(R4)] are (meth)acrylate monomers.
 4. The copolymeradditive of claim 1 wherein the copolymer additive further comprises areaction product of a thiol chain transfer agent.
 5. The copolymeradditive of claim 1 wherein 1 is chosen such that the copolymer additivecomprises about 5-50% by weight of [M^(L)].
 6. The copolymer additive ofclaim 1 wherein 1 is chosen such that the copolymer additive comprisesabout 10-40% by weight of [M^(L)].
 7. The copolymer additive of claim 1wherein q is chosen such that the copolymer additive has as OHequivalent weight ranging from about 200 g/equivalent hydroxyl groups to2000 g/equivalent hydroxyl groups.
 8. The copolymer additive of claim 1wherein q is chosen such that the copolymer additive has as OHequivalent weight ranging from about 250 g/equivalent hydroxyl groups to750 g/equivalent hydroxyl groups.
 9. The copolymer additive of claim 1wherein p is chosen such that the copolymer additive comprises about 1to 20% by weight [M^(A)].
 10. The copolymer additive of claim 1 whereinp is chosen such that the copolymer additive comprises 1.5 to 10% byweight [M^(A)].
 11. The copolymer additive of claim 1 wherein o ischosen such that the copolymer additive comprises about 5 to 80% byweight [M^(R4)].
 12. The copolymer additive of claim 1 wherein o ischosen such that the copolymer additive comprises 20 to 70% by weight[M^(R4)].
 13. The copolymer additive of claim 1 wherein o is chosen suchthat the copolymer additive comprises 10 to 50% by weight [M^(R4)]. 14.A coating composition comprising the copolymer additive of claim
 1. 15.The coating composition of claim 14 wherein the concentration of thecopolymer additive is no greater than 5 wt.-% solids of the coatingcomposition.
 16. A coating composition comprising the copolymer additiveof claim
 2. 17. The coating composition of claim 16 wherein theconcentration of the copolymer additive is no greater than 5 wt.-%solids of the coating composition.
 18. The coating composition of claim14 wherein the coating composition is a hardcoat after curing whereinthe hardcoat exhibits no more than 3 scratch when tested according tothe Steel Wool Abrasion Resistance test using a weight of 300 g and 10wipes.
 19. The coating composition of claim 16 wherein the coatingcomposition is a hardcoat after curing wherein the hardcoat exhibits nomore than 3 scratch when tested according to the Steel Wool AbrasionResistance test using a weight of 300 g and 10 wipes.